3-Arylbenzofuranones with electron-withdrawing substituents as stabilizers

ABSTRACT

The invention describes novel compounds of the formula (I) wherein the general symbols are as defined in claim (1) and R 1  is an aromatic radical with electron withdrawing substituents, as stabilizers for protecting organic materials, in particular polymers and lubricants, against oxidative, thermal or light-induced degradation and as scavengers for oxidized developer in color photographic material.

The present invention relates to novel 3-arylbenzofuranones, tocompositions comprising an organic material, preferably a polymer or alubricant, and to the novel stabilizers, as well as to the use thereoffor stabilizing organic materials against oxidative, thermal orlight-induced degradation and to the use of the novel stabilizers asscavengers for the oxidized developer (also termed hereafter Doxscavengers) in color photographic material.

It is well known that one of the problems associated with colorphotography is the diffusion of the oxidized color developer away fromthe light sensitive silver halide emulsion layer in which it is formedinto another silver halide emulsion layer, which can result in theformation of unwanted dyes at undesired places. For instance, whilebeing generated in the green sensitive layer and forming a magenta dyethrough a coupling reaction with the incorporated magenta coupler, theoxidized developer can also diffuse to the red sensitive layer therebyproducing unwanted cyan dye or to the blue sensitive layer therebyproducing unwanted yellow dye. This kind of color formation in the wronglayers will damage the color balance of the photographic image and thusresults in poor color reproduction. One way of circumventing thisproblem is to incorporate oxidized developer scavengers in interlayersbetween the light sensitive silver halide emulsion layers. Thesescavengers should have additional properties such as low tendency tomigrate, good stability towards aerial oxidation and high solubility inphotographic oils.

Hydroquinone derivatives which are useful as scavengers for oxidizeddevelopers are for example described in U.S. Pat. No. 4,345,016.

The use of some 3-phenyl-3H-benzofuran-2-ones as stabilizers for organicpolymers is disclosed, inter alia in WO-A-80/01566 and U.S. Pat. No.5,516,920.

It has now been found that a selected group of 3-arylbenzofuran-2-oneswith electron-withdrawing substituents is particularly suitable for useas stabilizers for organic materials that are susceptible to oxidative,thermal or light-induced degradation. These new compounds are alsoparticularly suitable as Dox scavengers in color photographic material.

Accordingly, the invention relates to compounds of the formula I

wherein, when n is 1,

R₁ is a radical of the formula II, III or IV

 and

when n is 2,

R₁ is

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,chloro, hydroxyl, C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino,di-(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino,C₃-C₂₅alkenoyloxy, C₃-C₂₅alkanoyloxy which is interrupted by oxygen,sulfur or

 C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy; or each pair of substituents R₂ and R₃ or R₃ and R₄ or R₄and R₅ together with the linking carbon atoms, forms a benzene ring; orR₄ is additionally —(CH₂)_(p)—COR₁₉ or —(CH₂)_(q)OH, or when R₃, R₅ andR₆ are hydrogen, R₄ is additionally a radical of the formula V

 wherein R₁ is as defined above for n=1,

R₆ is hydrogen or a radical of the formula VI

 in which R₄ is not a radical of the formula V and R₁ is as definedabove for n=1,

R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are each independently ofone another hydrogen, fluoro, fluoro-substituted C₁-C₁₂alkyl; —CN,

 —SOR₂₆, —SO₂R₂₆ or SO₃R₂₆; with the proviso that at least one of R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ or R₁₅ is not hydrogen,

R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene which are substituted by fluoro, fluoro-substitutedC₁-C₁₂alkyl, —CN,

 —SOR₂₆, —SO₂R₂₆ or SO₃R₂₆,

R₁₈ is hydrogen or C₁-C₈alkyl,

R₁₉ is hydroxyl,

 C₁-C₁₈alkoxy or

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃,C₁-C₁₂alkyl or phenyl, or R₂₀ and R₂₁ together with the linking carbonatom, form a C₅-C₈cycloalkylidene ring which is unsubstituted orsubstituted by 1 to 3 C₁-C₄alkyl groups;

R₂₂ is hydrogen, hydroxyl,

 C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; or

C₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

R₂₃ is C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

R₂₄ and R₂₅ are each independently of one another hydrogen, C₁-C₂₅alkyl,hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which is interrupted byoxygen, sulfur or

 phenylalkyl which is unsubstituted or is substituted on the phenyl ringby C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₂₄ and R₂₅, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring which is unsubstituted or is substituted by C₁-C₄alkylor is interrupted by oxygen, sulfur or

R₂₆ is hydrogen or C₁-C₂₅alkyl,

R₂₇ and R₂₈ are each independently of one another hydrogen, C₁-C₂₅alkyl,hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which is interrupted byoxygen, sulfur or

 C₇-C₉phenylalkyl which is unsubstituted or is substituted on the phenylring by C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₂₇ and R₂₈, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring which is unsubstituted or is substituted by C₁-C₄alkylor is interrupted by oxygen, sulfur or

R₂₉ and R₃₀ are each independently of one another hydrogen, C₁-C₁₈alkylor C₇-C₉phenylalkyl, or R₂₉ and R₃₀ together with the nitrogen atom towhich they are attached form a 5-, 6- or 7-membered heterocyclic ringwhich is unsubstituted or is substituted by C₁-C₄alkyl or is interruptedby oxygen, sulfur or

X₁ is a direct bond, C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interruptedby oxygen, sulfur or

 C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene, unsubstituted orC₁-C₄alkyl-substituted phenylene,

 or —O—X₃—O—,

X₂ is C₂-C₁₈alkylene, C₄-C₁₈alkylene which is interrupted by oxygen,sulfur or

 C₂-C₁₈alkenylene, C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene,unsubstituted or C₁-C₄alkyl-substituted phenylene,

X₃ is C₂-C₁₈alkylene, C₄-C₁₈alkylene which is interrupted by oxygen,sulfur or

 C₂-C₁₈alkenylene, C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene,unsubstituted or C₁-C₄alkyl-substituted phenylene,

M is a metal cation of valency r,

n is 1 or 2,

p is 0, 1 or 2,

q is 1, 2, 3, 4, 5 or 6, and

r is 1, 2 or 3.

Alkanoyloxy having up to 25 carbon atoms is a branched or unbranchedradical, for example formyloxy, acetoxy, propionyloxy, butanoyloxy,pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy,decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy,tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy,octadecanoyloxy, icosanoyloxy or docosanoyloxy. Preference is given toalkanoyloxy having from 2 to 18, especially from 2 to 12, e.g. from 2 to6, carbon atoms. Special preference is given to acetoxy.

C₃-C₂₅Alkanoyloxy interrupted by oxygen, sulfur or by

is, for example, CH₃—O—CH₂COO—, CH₃—S—CH₂COO—, CH₃—N(CH₃)—CH₂COO—,CH₃—O—CH₂CH₂—O—CH₂COO—, CH₃—(O—CH₂CH₂—)₂O—CH₂COO—,CH₃—(O—CH₂CH₂—)₃O—CH₂COO— or CH₃—(O—CH₂CH₂—)₄O—CH₂COO—.

C₆-C₉Cycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy,cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy.Preference is given to cyclohexylcarbonyloxy.

C₃-C₂₅Alkenoyloxy interrupted by oxygen, sulfur or by

is, for example, CH₃OCH₂CH₂CH═CHCOO— or CH₃OCH₂CH₂OCH═CHCOO—.

C₁-C₁₂Alkyl-substituted benzoyloxy, which carries preferably from 1 to3, especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethylbenzoyloxy,2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy,3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy,4-tert-butylbenzoyloxy, 2-ethylbenzoyloxy, 2,4,6-trimethylbenzoyloxy,2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy.Preferred substituents are C₁-C₈alkyl, especially C₁-C₄alkyl.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical,for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl,decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,icosyl or docosyl. One of the preferred definitions for R₂ and R₄ is,for example, C₁-C₁₈alkyl. An especially preferred definition for R₄ isC₁-C₄alkyl.

C₃-C₂₅Alkyl interrupted by oxygen, sulfur or by

is, for example, CH₃—O—CH₂CH₂—, CH₃—S—CH₂CH₂—, CH₃—N(CH₃)—CH₂CH₂—,CH₃—O—CH₂CH₂—O—CH₂CH₂—, CH₃—(O—CH₂CH₂—)₂O—CH₂CH₂—,CH₃—(O—CH₂CH₂—)₃O—CH₂CH₂— or CH₃—(O—CH₂CH₂—)₄O—CH₂CH₂—.

Fluoro-substituted C₁-C₁₂alkyl is a branched or unbranched radical, forexample fluoromethyl, difluoromethyl, trifluoromethyl orpentafluoroethyl. Trifluoromethyl is preferred.

C₇-C₉Phenylalkyl is, for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl andα,α-dimethylbenzyl.

C₇-C₉Phenylalkyl unsubstituted or substituted on the phenyl radical byfrom 1 to 3 C₁-C₄alkyl groups is, for example, benzyl, α-methylbenzyl,α,α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl,4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or4-tert-butylbenzyl. Preference is given to benzyl.

C₁-C₄Alkyl-substituted phenyl, which contains preferably from 1 to 3,especially 1 or 2, alkyl groups, is, for example, o-, m- orp-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl,2-ethylphenyl or 2,6-diethylphenyl.

Unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl is, for example,cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl,methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given tocyclohexyl and tert-butylcyclohexyl.

Alkoxy having up to 18 carbon atoms is a branched or unbranched radical,for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy,pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy,tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given toalkoxy having from 1 to 12, especially from 1 to 8, e.g. from 1 to 6,carbon atoms.

Alkylthio having up to 18 carbon atoms is a branched or unbranchedradical, for example methylthio, ethylthio, propylthio, isopropylthio,n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio,heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio oroctadecylthio. Preference is given to alkylthio having from 1 to 12,especially from 1 to 8, e.g. from 1 to 6, carbon atoms.

Alkylamino having up to 4 carbon atoms is a branched or unbranchedradical, for example methylamino, ethylamino, propylamino,isopropylamino, n-butylamino, isobutylamino or tert-butylamino.

Di(C₁-C₄alkyl)amino means also that the two radicals are eachindependently of the other branched or unbranched, for example,dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino,methylisopropylamino, methyl-n-butylamino, methylisobutylamino,ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino,ethyl-tert-butylamino, diethylamino, diisopropylamino,isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino ordi-isobutylamino.

Alkanoylamino having up to 25 carbon atoms is a branched or unbranchedradical, for example formylamino, acetylamino, propionylamino,butanoylamino, pentanoylamino, hexanoylamino, heptanoylamino,octanoylamino, nonanoylamino, decanoylamino, undecanoylamino,dodecanoylamino, tridecanoylamino, tetradecanoylamino,pentadecanoylamino, hexadecanoylamino, heptadecanoylamino,octadecanoylamino, icosanoylamino or docosanoylamino. Preference isgiven to alkanoylamino having from 2 to 18, especially from 2 to 12,e.g. from 2 to 6, carbon atoms.

C₁-C₁₈Alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene, dodecamethylene or octadecamethylene. A preferreddefinition for X₁ is C₁-C₁₂alkylene, especially C₁-C₈alkylene, forexample C₁-C₈alkylene. A preferred definition for X₂ is C₂-C₁₈alkylene,especially C₂-C₈alkylene. A preferred definition for X₃ isC₂-C₁₈alkylene, especially C₂-C₁₂alkylene, for example C₄-C₁₂alkylene.

C₂-C₁₈Alkylene interrupted by oxygen, sulfur or by

is, for example, —CH₂—O—CH₂—, —CH₂—S—CH₂—, —CH₂—N(CH₃)—CH₂—,—CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—, —CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—,—CH₂CH₂—(O—CH₂CH₂—)₂O—CH₂CH₂—, —CH₂CH₂—(O—CH₂CH₂—)₃O—CH₂CH₂—,—CH₂CH₂—(O—CH₂CH₂—)₄O—CH₂CH₂— or —CH₂CH₂—S—CH₂CH₂—.

Alkylidene having from 2 to 20 carbon atoms is, for example, ethylidene,propylidene, butylidene, pentylidene, 4-methylpentylidene, heptylidene,nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene,1-ethylpropylidene or 1-ethylpentylidene. Preference is given toC₂-C₈alkylidene.

Phenylalkylidene having from 7 to 20 carbon atoms is, for example,benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. Preference isgiven to C₇-C₉phenylalkylidene.

C₅-C₈Cycloalkylene is a saturated hydrocarbon group having two freevalences and at least one ring unit and is, for example, cyclopentylene,cyclohexylene, cycloheptylene or cyclooctylene. Preference is given tocyclohexylene.

C₇-C₈Bicycloalkylene is, for example, bicycloheptylene orbicyclooctylene.

Phenylene or naphthylene each unsubstituted or substituted byC₁-C₄alkyl, fluoro, trifluoromethyl or —CN is, for example, 1,2-, 1,3-or 1,4-phenylene; 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene;1,4-(2-trifluormethyl)phenylene, 1,4-(2-trifluormethyl)naphthylene or1,4-(2-cyano)phenylene.

A C₅-C₈cycloalkylidene ring substituted by C₁-C₄alkyl, which containspreferably from 1 to 3, especially 1 or 2, branched or unbranched alkylgroup radicals, is, for example, cyclopentylidene,methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene,methylcyclohexylidene, dimethylcyclohexylidene,trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene orcyclooctylidene. Preference is given to cyclohexylidene andtert-butylcyclohexylidene.

A mono-, di- or tri-valent metal cation is preferably an alkali metalcation, alkaline earth metal cation or aluminium cation, for exampleNa⁺, K⁺, Mg⁺⁺, Ca⁺⁺ or Al⁺⁺⁺.

Hydroxyl-substituted C₂-C₂₄alkyl is a branched or unbranched radicalwhich contains preferably 1 to 3, in particular 1 or 2, hydroxyl groups,such as, for example, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl,4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl,4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl,5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl,7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxyheptyl, 4-hydroxyheptyl,3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl,6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl,2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl,12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl,15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl,18-hydroxyoctadecyl, 20-hydroxyeicosyl or 22-hydroxydocosyl. A preferreddefinition of R₂₄, R₂₅, R₂₇ and R₂₈ is hydroxyl-substituted C₄-C₁₂alkyl,especially hydroxyl-substituted C₅-C₁₂alkyl, for examplehydroxyl-substituted C₅-C₁₁alkyl. One of the preferred definitions ofR₂₄, R₂₅ R₂₇ and R₂₈ is hydroxyl-substituted C₂-C₂₀alkyl, especiallyhydroxyl-substituted C₂-C₁₈alkyl, for example hydroxyl-substitutedC₂-C₁₄alkyl. A particularly preferred definition of R₂₄, R₂₅ R₂₇ and R₂₈is hydroxyl-substituted C₂-C₁₂alkyl, especially hydroxyl-substitutedC₂-C₈alkyl, for example hydroxyl-substituted C₂-C₄alkyl, such as2-hydroxyethyl, for example.

Alkenyl having 3 to 24 carbon atoms is a branched or unbranched radicalsuch as, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference isgiven to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6,especially 3 to 4 carbon atoms.

Where R₂₄ and R₂₅ or R₂₇ and R₂₈, together with the nitrogen atom towhich they are attached, form a 5-, 6- or 7-membered heterocyclic ringwhich is unsubstituted or is substituted by C₁-C₄alkyl or is interruptedby oxygen, sulfur or

this denotes, for example, the following radicals:

R₂₄ and R₂₅ or R₂₇ and R₂₈ preferably form, with the nitrogen atom towhich they are attached, a 6-membered heterocyclic ring interrupted byoxygen, such as, for example,

Where R₂₉ and R₃₀, together with the nitrogen atom to which they areattached, form a 5-, 6- or 7-membered heterocyclic ring which isunsubstituted or is substituted by C₁-C₄alkyl or is interrupted byoxygen, sulfur or

this denotes, for example, the following radicals:

C₂-C₁₈Alkenylene is, for example, vinylene, methylvinylene,octenylethylene or dodecenylethylene. C₂-C₈Alkenylene is preferred.

Preferred compounds of the formula I are those wherein,

when n is 1,

R₁ is a radical of the formula II, III or IV

 and

when n is 2,

R₁ is

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,chloro, hydroxyl, C₁-C₁₈-alkyl, C₇-C₉phenylalkyl, phenyl,C₅-C₈cycloalkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₁₈alkanoyloxy,C₁-C₁₈alkanoylamino, C₃-C₁₈alkenoyloxy, C₃-C₁₈alkanoyloxy which isinterrupted by oxygen or sulfur; C₆-C₉cycloalkylcarbonyloxy, benzoyloxyor C₁-C₄alkyl-substituted benzoyloxy; or each pair of substituents R₂and R₃ or R₃ and R₄ or R₄ and R₅ together with the linking carbon atoms,forms a benzene ring; or R₄ is additionally —(CH₂)_(p)—COR₁₉ or—(CH₂)_(q)OH, or when R₃, R₅ and R₆ are hydrogen, R₄ is additionally aradical of the formula V

 wherein R₁ is as defined above for n=1,

R₆ is hydrogen or a radical of the formula VI

 in which R₄ is not a radical of the formula V and R₁ is as definedabove for n=1,

R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are each independently ofone another hydrogen, fluoro, fluoro-substituted C₁-C₈alkyl; —CN,

 —SOR₂₆, —SO₂R₂₆ or SO₃R₂₆; with the proviso that at least one of R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ or R₁₅ is not hydrogen,

R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene which are substituted by fluoro, trifluoromethyl, —CN,

 —SOR₂₆, —SO₂R₂₆ or SO₃R₂₆,

R₁₈ is hydrogen or C₁-C₄alkyl,

R₁₉ is hydroxyl,

 C₁-C₁₈alkoxy or

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃,C₁-C₈alkyl or phenyl, or R₂₀ and R₂₁ together with the linking carbonatom, form a C₅-C₈cycloalkylidene ring;

R₂₂ is hydrogen, hydroxyl,

 C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, C₅-C₈-cycloalkyl; or C₃-C₂₅alkylwhich is interrupted by oxygen or sulfur,

R₂₃ is C₁-C₂₂alkyl, C₇-C₉phenylalkyl, phenyl, C₅-C₈cycloalkyl orC₃-C₂₅alkyl which is interrupted by oxygen or sulfur,

R₂₄ and R₂₅ are each independently of one another hydrogen, C₁-C₁₈alkyl,hydroxyl-substituted C₂-C₁₈alkyl; C₃-C₁₈alkyl which is interrupted byoxygen, sulfur or

 phenylalkyl, or C₃-C₁₈alkenyl; or R₂₄ and R₂₅, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring,

R₂₆ is hydrogen or C₁-C₁₈alkyl,

R₂₇ and R₂₈ are each independently of one another hydrogen, C₁-C₁₈alkyl,hydroxyl-substituted C₂-C₁₈alkyl; C₃-C₁₈alkyl which is interrupted byoxygen, sulfur or

 phenylalkyl, or C₃-C₁₈alkenyl; or R₂₇ and R₂₈, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring,

R₂₉ and R₃₀ are each independently of one another hydrogen, C₁-C₁₈alkylor C₇-C₉phenylalkyl, or R₂₉ and R₃₀ together with the nitrogen atom towhich they are attached form a 5-, 6- or 7-membered heterocyclic ring,

X₁ is a direct bond, C₁-C₁₂alkylene, C₂-C₁₈alkylene which is interruptedby oxygen or sulfur, C₂-C₁₂alkenylene, C₂-C₁₂alkylidene,C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene, phenylene,

 or —O—X₃—O—,

X₂ is C₂-C₁₂alkylene, C₄-C₁₂alkylene which is interrupted by oxygen,sulfur or

 C₂-C₁₂alkenylene, C₅-C₈cycloalkylene, phenylene,

X₃ is C₂-C₁₈alkylene, C₄-C₁₂alkylene which is interrupted by oxygen,sulfur or

 C₂-C₁₂alkenylene, C₅-C₈cycloalkylene, phenylene,

M is a metal cation of valency r,

n is 1 or 2,

p is 0, 1 or 2,

q is 1, 2, 3, 4, 5 or 6, and

r is 1, 2 or 3.

Further preferred compounds of the formula I are those wherein,

when n is 1,

R₁ is a radical of the formula II, III or IV, and

when n is 2,

R₁ is

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl, C₁-C₁₂alkoxy,C₁-C₁₂alkylthio, C₁-C₁₂alkanoyloxy, C₃-C₁₂alkenoyloxy, C₃-C₁₂alkanoyloxywhich is interrupted by oxygen; cyclohexylcarbonyloxy, benzoyloxy oreach pair of substituents R₂ and R₃ or R₃ and R₄ or R₄ and R₅ togetherwith the linking carbon atoms, forms a benzene ring; or R₄ isadditionally —(C₂)_(p)—COR₁₉ or —(CH₂)_(q)OH, or when R₃, R₅ and R₆ arehydrogen, R₄ is additionally a radical of the formula V, wherein R₁ isas defined above for n=1,

R₆ is hydrogen or a radical of the formula VI in which R₄ is not aradical of the formula V and R₁ is as defined above for n=1,

R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are each independently ofone another hydrogen, fluoro, fluoro-substituted C₁-C₄alkyl; —CN,

 —SOR₂₆, —SO₂R₂₆ or SO₃R₂₆; with the proviso that at least one of R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ or R₁₅ is not hydrogen,

R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene,

R₁₉ is hydroxyl, C₁-C₁₈alkoxy or

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃ orC₁-C₄alkyl, or R₂₀ and R₂₁ together with the linking carbon atom, form acyclohexylidene ring;

R₂₂ is hydroxyl, C₁-C₁₂alkyl, phenyl, cyclohexyl or C₃-C₁₂alkyl which isinterrupted by oxygen,

R₂₃ is C₁-C₂₂alkyl, benzyl, phenyl, cyclohexyl or C₃-C₁₂alkyl which isinterrupted by oxygen,

R₂₄ and R₂₅ are each independently of one another hydrogen, C₁-C₁₂alkyl,hydroxyl-substituted C₂-C₁₂alkyl; C₃-C₁₂alkyl which is interrupted byoxygen; benzyl or C₃-C₁₂alkenyl; or R₂₄ and R₂₅, together with thenitrogen atom to which they are attached, form 6-membered heterocyclicring,

R₂₆ is C₁-C₁₂alkyl,

R₂₇ and R₂₈ are each independently of one another hydrogen, C₁-C₁₂alkyl,hydroxyl-substituted C₂-C₁₂alkyl; C₃-C₁₈alkyl which is interrupted byoxygen; benzyl or C₃-C₁₂alkenyl; or R₂₇ and R₂₈, together with thenitrogen atom to which they are attached, form 6-membered heterocyclicring,

R₂₉ and R₃₀ are each independently of one another hydrogen, C₁-C₁₂alkylor benzyl, or R₂₉ and R₃₀ together with the nitrogen atom to which theyare attached form a 6-membered heterocyclic ring,

X₁ is a direct bond, C₁-C₈alkylene, C₂-C₁₈alkylene which is interruptedby oxygen; phenylene,

 or —O—X₃—O—,

X₂ is C₂-C₈alkylene, C₄-C₁₂alkylene which is interrupted by oxygen;cyclohexylene, phenylene,

X₃ is C₂-C₁₈alkylene, C₄-C₁₂alkylene which is interrupted by oxygen;C₂-C₁₂alkenylene, cyclohexylene, phenylene,

n is 1 or 2,

p is 1 or 2, and

q is 2 or 3.

Also preferred are compounds of the formula I

wherein, when n is 1,

R₁ is a radical of the formula II, and

when n is 2,

R₁ is

R₂ is hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl,C₁-C₈alkanoyloxy or benzoyloxy,

R₃ is hydrogen or C₁-C₄alkyl,

R₄ is hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl,C₁-C₈alkanoyloxy, —(CH₂)_(p)—COR₁₉ or —(CH₂)_(q)OH, or when R₃, R₅ andR₆ are hydrogen, R₄ is additionally a radical of the formula V, whereinR₁ is as defined above for n=1,

R₅ is hydrogen or C₁-C₄alkyl,

R₆ is hydrogen or a radical of the formula VI in which R₄ is not aradical of the formula V and R₁ is as defined above for n=1,

R₇, R₈, R₉, R₁₀ and R₁₁ are each independently of one another hydrogen,fluoro, fluoro-substituted C₁-C₄alkyl; —CN,

 —SOR₂₆, or —SO₂R₂₆; with the proviso that at least one of R₇, R₈, R₉,R₁₀ or R₁₁ is not hydrogen,

R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene,

R₁₉ is C₁-C₈alkoxy,

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃ orC₁-C₄alkyl, or R₂₀ and R₂₁ together with the linking carbon atom, form acyclohexylidene ring;

R₂₃ is C₁-C₂₂alkyl, benzyl, phenyl, cyclohexyl or C₃-C₁₂alkyl which isinterrupted by oxygen,

R₂₄ and R₂₅ are each independently of one another hydrogen, C₁-C₄alkyl,hydroxyl-substituted C₂-C₄alkyl; C₃-C₁₂alkyl which is interrupted byoxygen; benzyl or C₃-C₁₂alkenyl,

R₂₆ is C₁-C₈alkyl,

R₂₉ and R₃₀ are each independently of one another hydrogen, C₁-C₈alkylor benzyl,

X₁ is a direct bond, C₁-C₈alkylene,

X₂ is C₂-C₈alkylene or C₄-C₁₂alkylene which is interrupted by oxygen,

X₃ is C₂-C₁₈alkylene or C₄-C₁₂alkylene which is interrupted by oxygen,

n is 1 or 2,

p is 1 or 2, and

q is 2 or 3.

Particularly interesting compounds of the formula I are those wherein,

when n is 1,

R₁ is a radical of the formula II, and

when n is 2,

R₁ is

R₂ is C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl or cyclohexyl,

R₃ is hydrogen or methyl,

R₄ is hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl or aradical of the formula V, wherein R₁ is as defined above for n=1,

R₅ is hydrogen or methyl,

R₆ is hydrogen or a radical of the formula VI in which R₄ is not aradical of the formula V and R₁ is as defined above for n=1,

R₇, R₈, R₉, R₁₀ and R₁₁ are each independently of one another hydrogen,fluoro, fluoro-substituted C₁-C₄alkyl; —CN,

 —SOR₂₆, or —SO₂R₂₆; with the proviso that at least one of R₇, R₈, R₉,R₁₀ or R₁₁ is not hydrogen,

R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene,

R₂₀ and R₂₁ are each independently of one another hydrogen orC₁-C₄alkyl, or R₂₀ and R₂₁ together with the linking carbon atom, form acyclohexylidene ring;

R₂₃ is C₁-C₂₂alkyl, benzyl, phenyl, cyclohexyl or C₃-C₁₂alkyl which isinterrupted by oxygen,

R₂₆ is C₁-C₈alkyl,

X₁ is a direct bond, C₁-C₈alkylene or —O—X₃—O—,

X₃ is C₂-C₁₈alkylene or C₄-C₁₂alkylene which is interrupted by oxygen,and

n is 1 or 2.

Compounds of the formula I of very particular interest are thosewherein,

when n is 1,

R₁ is a radical of the formula II, and

when n is 2,

R₁ is

R₂ is C₁-C₈alkyl or cyclohexyl,

R₃ is hydrogen,

R₄ is hydrogen, C₁-C₈alkyl, cyclohexyl or a radical of the formula V,wherein R₁ is as defined above for n=1,

R₅ is hydrogen,

R₆ is hydrogen or a radical of the formula VI in which R₄ is not aradical of the formula V and R₁ is as defined above for n=1,

R₇, R₈, R₉, R₁₀ and R₁₁ are each independently of one another hydrogen,fluoro, trifluoromethyl; —CN or

 with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ is nothydrogen,

R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene,

R₂₀ and R₂₁ are each independently of one another hydrogen orC₁-C₄alkyl, or R₂₀ and R₂₁ together with the linking carbon atom, form acyclohexylidene ring;

R₂₃ is C₁-C₂₂alkyl, benzyl or cyclohexyl,

X₁ is C₁-C₈alkylene or —O—X₃—O—,

X₃ is C₂-C₁₄alkylene, and

n is 1 or 2.

Very particularly preferred compounds of the formula I are those wherein

when n is 1,

R₁ is a radical of the formula II, and

when n is 2,

R₁ is

R₂ is C₁-C₄alkyl,

R₃ is hydrogen,

R₄ is C₁-C₄alkyl,

R₅ is hydrogen,

R₆ is hydrogen or a radical of the formula VI wherein R₁ is as definedabove for n=1,

R₇ is hydrogen or trifluoromethyl,

R₈ is hydrogen, trifluoromethyl or —CN,

R₉ is hydrogen or trifluoromethyl,

R₁₀ is hydrogen, trifluoromethyl or —CN,

R₁₁ is hydrogen, fluoro, trifluoromethyl, —CN or

 with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ is nothydrogen,

R₁₆ and R₁₇ are phenylene or naphthylene,

R₂₃ is C₁-C₂₂alkyl,

X₁ is —O—X₃—O—,

X₃ is C₄-C₁₂alkylene, and

n is 1 or 2.

The compounds of the formula I can be prepared in per se known manner. Apreferred process for the preparation of the compounds of the formula Iis disclosed in WO-A-99/67232.

The compounds of the formula I are suitable for stabilizing organicmaterials against oxidative, thermal or light-induced degradation.Special attention is drawn to their excellent action as antioxidants inthe stabilization of organic materials.

Illustrative examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

Further objects of the invention are therefore compositions comprisinga) an organic material that is susceptible to oxidative, thermal orlight-induced degradation, and b) at least one compound of the formulaI.

Preferred organic materials are natural, semi-synthetic or, preferably,synthetic polymers.

Particularly referred organic materials are synthetic polymers, mostpreferably thermoplastic polymers. Especially preferred organicmaterials are polyacetals, polyolefins such as polypropylene orpolyethylene, polyether/polyurethanes, polyesters such as polybutyleneterephthalate, polycarbonates or vulcanisates,

To be singled out for special mention is the efficacy of the novelcompounds of the formula I against oxidative or thermal degradation,especially under the action of heat which occurs during the processingof thermoplasts. The compounds of the formula I of this invention aretherefore admirably suited for use as processing stabilizers.

The compounds of the formula I will preferably be added to the organicmaterial to be stabilized in concentrations of 0.0005 to 10%, preferably0.001 to 2%, typically 0.01 to 2%, based on the weight of said material.

In addition to comprising the compounds of the formula I, the inventivecompositions may comprise further co-stabilizers, typically thefollowing:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosohonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂₂, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzoyl)-malonate,3n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyl-oxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)-ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylpentyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxyltridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicycloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecylnitrone,N-hexadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A4316611;DE-A4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7di-tert-butylbenzofuran-2-one.

The co-stabilizers are typically used in concentrations of 0.01 to 10%,based on the total weight of the material to be stabilized.

The novel compounds of the formula I can be used in particular togetherwith phenolic antioxidants, light stabilizers and/or processingstabilizers.

Other preferred compositions comprise, in addition to compounds of theformula I, a compound of the organic phosphite or phosphonite type.

The fillers and reinforcing agents (point 12 of the list), such as, forexample, talc, calcium carbonate, mica or kaolin, are added to thepolyolefins, for example, in concentrations of from 0.01 to 40%, basedon the total weight of the polyolefins to be stabilized.

The fillers and reinforcing agents (point 12 of the list), such as, forexample, metal hydroxides, especially aluminium hydroxide or magnesiumhydroxide, are added to the polyolefins, for example, in concentrationsof from 0.01 to 60%, based on the total weight of the polyolefins to bestabilized.

Carbon black, as filler, is added to the polyolefins advantageously inconcentrations of from 0.01 to 5%, based on the total weight of thepolyolefins to be stabilized.

Glass fibres, as reinforcing agents, are added to the polyolefinsadvantageously in concentrations of from 0.01 to 20%, based on the totalweight of the polyolefins to be stabilized.

Also of interest as yet further additives in the compositions accordingto the invention are alkaline earth metal salts of higher fatty acids,such as, for example, calcium stearate; calcium lactate and/or calciumstearoyl-2-lactylate.

As a conventional stabilizer combination for the processing of polymericorganic materials, such as, for example, polyolefins, into correspondingmoulded articles, the combination of a phenolic antioxidant with asecondary antioxidant based on an organic phosphite or phosphonite isrecommended. Depending on the substrate and process, however, manypolyolefin processors are obliged to operate processes in thehigh-temperature range above approx. 280° C. The inclusion of aprocessing stabilizer of the formula I is particularly suitable forhigh-temperature applications, especially in the temperature range above300° C. Technical materials and moulded articles for instance based onHD polyethylene, such as, for example, pipes and their technicalvariants (fittings), can be manufactured with a higher output and fewerrejects. A further advantage of the compounds of the formula I is alsothat they can be used in a very small amount, which results in areduction in the overall antioxidant concentration compared withconventional stabilizer mixtures. For instance the use of a lowconcentration of a compound of the formula I allows the overallstabilizer concentration to be reduced by approximately a third in, forexample, polyolefins, which at the same time represents an economicadvantage.

The compounds of the formula I and other optional additives areincorporated into the organic polymeric material according to knownmethods, for example before or during shaping to moulded articles oralternatively by coating the organic polymeric material with a solutionor dispersion of the compounds and subsequently evaporating the solvent.The compounds of the formula I can also be added to the materials to bestabilized in the form of a master batch which contains these compounds,typically in a concentration of, for example, from 2.5 to 25% by weight.

The compounds of the formula I may also be added before or duringpolymerization or before crosslinking.

In this connection, particular attention is drawn to the surprisingfeature that the novel compounds of the formula I inhibit discoloration,especially so-called pinking in the manufacture of e.g. polyurethanefoams.

The compounds of the formula I, and where applicable further additives,may be incorporated into the material to be stabilized in pure form orencapsulated in waxes, oils or polymers.

The compounds of the formula I, and where applicable further additives,may also be sprayed onto the polymer to be stabilized. They are able tobe used to dilute other additives (e.g. the above-mentioned conventionaladditives) or melts thereof, so that they can also be sprayed togetherwith these additives onto the polymer to be stabilized. Application byspraying during the deactivation of the polymerization catalysts isespecially advantageous, in which case spraying is conveniently effectedwith the vapour used for deactivation.

The materials stabilized in that manner may be used in an extremely widevariety of forms, e.g. in the form of films, fibres, tapes, mouldingcompounds or profiles, or as binders for surface-coatings, especiallypowder coatings, adhesives or cements.

The polyolefins stabilized in that manner may likewise be used in anextremely wide variety of forms, especially in the form of thick-layerpolyolefin moulded articles that are in lasting contact with extractingmedia, such as, for example, pipes for liquids or gases, films, fibres,geomembranes, tapes, profiles or tanks.

The preferred thick-layer polyolefin moulded articles have a layerthickness of from 1 to 50 mm, especially from 1 to 30 mm, e.g. from 2 to10 mm.

A preferred embodiment of this invention is therefore the use ofcompounds of the formula I for stabilizing organic materials againstoxidative, thermal or light-induced degradation.

The invention also relates to a process for stabilizing an organicmaterial against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein or applying thereto at least onecompound of the formula I.

The invention relates also to compositions comprising a functionalfluid, preferably from the series of lubricants, hydraulic fluids andmetal-working fluids and also fuels for powering engines of the4-stroke, Otto, 2-stroke, diesel, Wankel and orbital types, and at leastone compound of the formula I.

The compounds of the formula I may preferably be used in lubricants andfuels as multi-functional stabilizers, that is to say they combine inthemselves antioxidative, friction-reducing, extreme-pressure-protectionand wear-protection action and also anti-corrosion properties.

Preferred lubricants and fuels and related products are engine oils,turbine oils, gear oils, hydraulic fluids, diesel or Otto fuels,metal-working fluids and lubricating greases.

Especially preferred lubricants are mineral oils, synthetic oils ormixtures thereof.

Products known per se are used as functional fluids from the series oflubricants, hydraulic fluids and metal-working fluids.

The lubricants and hydraulic fluids that come into consideration will befamiliar to the person skilled in the art and are described in therelevant specialist literature, such as, for example, in Dieter Klamann,“Schmierstoffe und verwandte Produkte” [Lubricants and related products](Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, “DasSchmiermittel-Taschenbuch” [The lubricant handbook] (Dr. AlfredHüthig-Verlag, Heidelberg, 1974) and in “Ullmanns Enzyklopädie dertechnischen Chemie” [Ullmann's Encyclopaedia of Industrial Chemistry],Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

The lubricants are especially oils and greases, for example based on amineral oil. Oils are preferred.

A further group of lubricants that may be used are vegetable or animaloils, greases, tallows and waxes or mixtures thereof with one another ormixtures with the mentioned mineral or synthetic oils.

Vegetable and animal oils, greases, tallows and waxes are, for example,palm-kernel oil, palm oil, olive oil, rapeseed oil, rape oil, linseedoil, groundnut oil, soybean oil, cottonseed oil, sunflower oil, pumpkinseed oil, coconut oil, maize oil, castor oil, tree nut oil and mixturesthereof, fish oils, tallows obtained from slaughtered animals, such asbeef tallow, neatsfoot oil and bone oil, and modified, epoxidised andsulfoxidised forms thereof, for example epoxidised soybean oil.

The mineral oils are based especially on hydrocarbon compounds.

Examples of synthetic lubricants include lubricants based on aliphaticor aromatic carboxy esters, polymeric esters, polyalkylene oxides,phosphoric acid esters, poly-alpha-olefins or silicones, a diester of adivalent acid with a monohydric alcohol, such as, for example, dioctylsebacate or dinonyl adipate, a triester of trimethylolpropane with amonovalent acid or with a mixture of such acids, such as, for example,trimethylolpropane tripelargonate, trimethylolpropane tricaprylate ormixtures thereof, a tetraester of pentaerythritol with a monovalent acidor with a mixture of such acids, such as, for example, pentaerythritoltetracaprylate, or a complex ester of monovalent and divalent acids withpolyhydric alcohols, for example a complex ester of trimethylolpropanewith caprylic and sebacic acid, or a mixture thereof. Apart from mineraloils there are especially suitable, for example, poly-alpha-olefins,ester-based lubricants, phosphates, glycols, polyglycols andpolyalkylene glycols, and also mixtures thereof with water.

Metal-working fluids and hydraulic fluids may be prepared on the basisof the same substances as those described above for the lubricants, suchfluids frequently being emulsions of such substances in water or otherliquids.

Lubricant and fuel compositions according to the invention are used, forexample, in internal combustion engines, e.g. in motorised vehiclesequipped with, for example, engines of the Otto, diesel, two-stroke,Wankel or orbital type.

The compounds of the formula I are readily soluble in lubricants andfuels, metal-working fluids and hydraulic fluids and are thereforeespecially suitable as additives for lubricants and fuels, metal-workingfluids and hydraulic fluids.

As additives in lubricants, the compounds of the formula I are effectiveeven in very small amounts. They are mixed in with the lubricantsadvantageously in an amount of from 0.01 to 5% by weight, preferably inan amount of from 0.05 to 3% by weight and very especially in an amountof from 0.1 to 2% by weight, in each case based on the lubricant.

The compounds of the formula I may be mixed in with the lubricants andfuels in a manner known per se. The compounds of the formula I arereadily soluble, for example, in oils. It is also possible to prepare aso-called master batch, which may be diluted, as a function of use, withthe appropriate lubricant or fuel to the concentrations suitable foruse. In such cases concentrations above 1% by weight are possible.

The lubricants and fuels, metal-working fluids and hydraulic fluids mayadditionally comprise other additives that are added in order to improvetheir basic properties still further; such additives include: furtherantioxidants, metal passivators, rust inhibitors, viscosity indeximprovers, pour-point depressants, dispersants, detergents, coefficientof friction reducers, further extreme-pressure additives and anti-wearadditives. Such further additives are added advantageously in an amountof from 0.01 to 5% by weight.

A number of such compounds can be found, for example, in the above list“1. Antioxidants”, especially points 1.1 to 1.19. In addition, furtheradditives may be mentioned by way of example:

Examples of Further Antioxidants:

Aliphatic or aromatic phosphites, esters of thiodipropionic add orthiodiacetic acid or salts of dithiocarbamic or dithiophosphoric acid,2,2,12,12-tetramethyl-5,9-dihydroxy-3,7,11-trithiatridecane and2,2,15,15-tetramethyl-5,12-dihydroxy-3,7,10,14-tetrathiahexadecane.

Examples of Metal Deactivators, e.g. for Copper, are:

a) Benzotriazoles and derivatives thereof, e.g. 2-mercaptobenzotriazole,2,5-dimercaptobenzotriazole, 4- or 5-alkylbenzotriazoles (e.g.tolutriazole) and derivatives thereof, 4,5,6,7-tetrahydrobenzotriazole,5,5′-methylenebis-benzotriazole; Mannich bases of benzotriazole ortolutriazole, such as 1-[di(2-ethylhexyl)aminomethyl]tolutriazole and1-[di(2-ethylhexyl)aminomethyl]benzotriazole; alkoxyalkylbenzotriazoles,such as 1-(nonyloxymethyl)benzotriazole, 1-(1-butoxyethyl)benzotriazoleand 1-(1-cyclohexyloxybutyl)tolutriazole.

b) 1,2,4-Triazoles and derivatives thereof, e.g. 3-alkyl- (or-aryl-)1,2,4-triazoles, Mannich bases of 1,2,4-triazoles, such as1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole;alkoxyalkyl-1,2,4-triazoles, such as 1-(1-butoxyethyl)-1,2,4-triazole;acylated 3-amino-1,2,4-triazoles.

c) Imidazole derivatives, e.g.4,4′-methylenebis(2-undecyl-methyl)imidazole andbis[(N-methyl)imidazol-2-yl]carbinol-octyl ether.

d) Sulfur-containing heterocyclic compounds, e.g.2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole,2,5-dimercaptobenzothiadiazole and derivatives thereof;3,5-bis-[di(2-ethylhexyl)aminomethyl]-1,3,4-thiadiazolin-2-one.

e) Amino compounds, e.g. salicylidene-propylenediamine,salicylaminoguanidine and salts thereof.

Examples of Rust Inhibitors are:

a) Organic acids, their esters, metal salts, amine salts and anhydrides,e.g. alkyl- and alkenyl-succinic acids and their partial esters withalcohols, diols or hydroxycarboxylic acids, partial amides of alkyl- andalkenyl-succinic acids, 4-nonylphenoxyacetic acid, alkoxy- andalkoxyethoxy-carboxylic acids, such as dodecyloxyacetic acid,dodecyloxy(ethoxy)acetic acid and amine salts thereof, and alsoN-oleoyl-sarcosine, sorbitan monoxoleate, lead naphthenate,alkenylsuccinic acid anhydrides, e.g. dodecenylsuccinic acid anhydride,2-(2-carboxyethyl)-1-dodecyl-3-methylgycerol and salts thereof,especially sodium and triethanolamine salts thereof.

b) Nitrogen-containing compounds, e.g.:

i. Primary, secondary or tertiary, aliphatic or cycloaliphatc amines andamine salts of organic and inorganic acids, e.g. oil-solublealkylammonium carboxylates, and1-[N,N-bis(2-hydroxyethyl)amino]-3-(4-nonylphenoxy)propan-2-ol.

ii. Heterocyclic compounds, e.g.: substituted imidazolines andoxazolines, e.g. 2-heptadecenyl-1-(2-hydroxyethyl)imidazoline.

c) Phosphorus-containing compounds, e.g.:

Amine salts of phosphoric acid partial esters or phosphonic acid partialesters, zinc dialkyldithiophosphates.

d) Sulfur-containing compounds, e.g.:

Barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates,alkylthio-substituted aliphatic carboxylic acids, esters of aliphatic2-sulfocarboxylic acids and salts thereof.

e) Glycerol derivatives, e.g.:

Glycerol monooleate, 1-(alkylphenoxy)-3-(2-hydroxyethyl)glycerols,1-(alkylphenoxy)-3-(2,3-dihydroxypropyl)glycerols,2-carboxyalkyl-1,3-dialkylglycerols.

Examples of Viscosity Index Improvers are:

Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylatecopolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers,styrene/acrylate copolymers, polyethers.

Examples of Pour-point Depressants are:

Poly(meth)acrylates, ethylene/vinyl acetate copolymer,alkylpolystyrenes, fumarate copolymers, alkylated naphthalenederivatives.

Examples of Dispersants/surfactants are:

Polybutenylsuccinic acid amides or imides, polybutenylphosphonic acidderivatives, basic magnesium, calcium and barium sulfonates andphenolates.

Examples of Extreme-pressure and Anti-wear Additives are:

Sulfur- and/or phosphorus- and/or halogen-containing compounds, such as,for example, chlorinated paraffins, sulfurated olefins or vegetable oils(soybean/rape oil), alkyl- or aryl-di- or -tri-sulfides, zincdialkyldithiophosphates, zinc dithiocarbamates such as zincdiamyldithiocarbamate, molybdenum dithioates such as molybdenumdithiocarbamates, triaryl phosphates such as tritolyl phosphate,tricresyl phosphate, phenyl phosphate isopropyl ester, amine salts ofmono- or di-alkylphosphoric acids such as the amine salts ofmono-/di-hexyl phosphate, amine salts of alkylphosphonic acids such asthe amine salt of methylphosphonic acid, triaryl phosphites such astris[nonylphenyl] phosphite, dialkyl phosphites such as dioctylphosphite, triaryl monothiophosphates such as triphenyl thionophosphateor tris[isononylphenyl] thionophosphate or tert-butylated triphenylthionophosphate, substituted trialkyl mono- or di-thiophosphates such asdiisopropoxyphosphinothioyl)thio]propionate orbutylene-1,3-bis[(diisobutoxyphosphinothioyl)propionate,trithiophosphates such as trithiophosphoric acidS,S,S-tris(isooctyl-2-acetates), amine salts of3-hydroxy-1,3-thiaphosphetane-3-oxide, benzotriazoles or derivativesthereof such as bis(2-ethylhexyl)aminomethyltolutriazole,dithiocarbamates such as methylene-bis-dibutyldithiocarbamate,derivatives of 2-mercaptobenzothiazole such as1-[N,N-bis(2-ethylhexyl)aminomethyl]-2-mercapto-1H-1,3-benzothiazole,derivatives of 2,5-dimercapto-1,3,4-thiadiazole such as2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole.

Examples of Coefficient of Friction Reducers are:

Lard oil, oleic acid, tallow, rape oil, sulfurated fats, amines. Furtherexamples are given in EP-A-0 565 487.

Examples of Special Additives for use in Water/oil Metal-working Fluidsand Hydraulic Fluids are:

Emulsifiers: petroleum sulfonates, amines, such as polyoxyethylatedfatty amines, non-ionic surface-active substances;

buffers: alkanolamines;

biocides: triazines, thiazolinones, tris-nitromethane, morpholine,sodium pyridenethol;

speed improvers: calcium and barium sulfonates;

Examples of Fuel Additives:

Fuel additives are described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Vol 12, 1994 and in this instance are essentially petrol anddiesel additives:

Petrol: dyes, especially azo dyes;

Antioxidants: aminic, especially para-phenylenediamines, or phenolic,e.g. 2,6-di-tert-butylphenol, as described above;

Metal deactivators: especially N,N′-disalicylidene-1,2-propane,benzotriazole, EDTA;

Rust inhibitors: for example carboxylic acids, sulfonates, amines oramine salts;

Dispersants: e.g. esters, high-molecular-weight amines, Mannich bases,succinimides, borated succinimides;

Detergents: for example fatty acid amides, nonpolymeric amines,polybutene succinimides, polyether amines, low-molecular-weight amines,sulfonates, salicylic acid derivatives;

Demulsifiers: for example long-chain alcohols or phenols containingpoly-ethylene or -butylene groups;

Antiknock agents: tetralkyl lead, manganesemethylcyclopentadienyltricarbonyl;

Oxygen compounds: esters of vegetable oils, ethers, alcohols forimproving burn behaviour;

Diesel: ignition improvers (cetane improvers), e.g. alkyl nitrates,ether nitrates, alkyl diglycol nitrates, organic peroxides;

Stabilizers for, especially, cracked diesel: amines and otherN-containing compounds that act as radical traps.

Especially preferred further additives in lubricants are aminicantioxidants, especially mixtures of mono- and di-alkylatedtert-butyl-/tert-octyl-diphenylamines.

The present invention relates also to the use of the components of theformula I for stabilizing organic materials, especially as additives inlubricants and fuels, hydraulic fluids or metal-working fluids,preferably in hydraulic oils and gear oils. The use according to theinvention includes protection of the metal components to be lubricatedagainst mechanical attrition (wear protection) and corrosion protectionactivity and also antioxidation activity—with respect both to thelubricant and to the metal components.

The present invention accordingly relates also to a method for improvingthe properties, during use, of organic materials, especially lubricantsand fuels, metal-working fluids and hydraulic fluids, wherein a compoundof the formula I is added to those materials.

The photographic materials according to this invention comprise asupport bearing at least one layer of a light-sensitive silver halideemulsion.

Examples of color photographic materials according to this invention arecolor negative films, color reversal films, color positive films, colorphotographic paper, color reversal photographic paper, color-sensitivematerials for the dye diffusion transfer process or the silver dyebleach process.

Of especial interest is a color photographic recording materialcomprising, on a base, at least one blue-sensitive silver halideemulsion layer containing at least one yellow dye providing compound, atleast one green-sensitive silver halide emulsion layer containing atleast one magenta dye providing compound, at least one red-sensitivesilver halide emulsion layer containing at least one cyan dye providingcompound, and customary (non light sensitive) top layer(s) andinterlayers separating the light-sensitive layers.

The layers of the color photographic material can be arranged in variousorders as is well known in the art.

The compounds of the formula I can be contained in any of the layers ofthe photographic material, i.e. in any of the light sensitive silverhalide emulsion layers or in a non light sensitive layer. For use as aDox scavenger, the compound of the formula I is preferably contained inone or more non light sensitive layers. In this case, the lightsensitive layers may contain a lower concentration of a compound of theformula I or none.

The compounds of the formula I are preferably incorporated in aninterlayer, especially a non-photosensitive interlayer, adjacent to thegreen-sensitive layer containing a magenta coupler. Preferred colorphotographic materials within this invention are those wherein themagenta coupler is of the pyrazolo-azole type, e.g. as disclosed in U.S.Pat. No. 5,538,840, column 49, line 51, until column 69, line 27, andpublications cited therein; this section of U.S. Pat. No. 5,538,840 ishereby incorporated by reference.

Also preferred is a color photographic material, wherein the silverhalide emulsion contains at least 95 mol-% AgCl.

In general, the compounds of the formula I are contained in thephotographic material in an amount from 10 to 1000 mg/m², especiallyfrom 30 to 500 mg/m².

The compounds of formula I can be milled with polymers (e.g. PVS,polyester, polyvinyl alcohol etc.) and placed in a layer thus preventingtheir migration to adjacent layers. Also, compounds of formula Icontaining a suitable functional group (e.g. ester, hydroxy) can bereacted with a polymer, e.g. a polyvinyl alcohol or polyester, in orderto attach them chemically. This form will reduce their migratingtendency.

Typical bases for the photographic material include polymeric films andpaper (including polymer-coated paper). Details regarding supports andother layers of color photographic recording materials can be found inResearch Disclosure, Item 36544, September 1994.

Essential constituents of the photographic emulsion layers are binders,silver halide particles and color couplers. Details regarding theconstituents of the light sensitive layers and other (non lightsensitive) layers such as top layers and interlayers separating thesilver halide emulsion layers can be found in Research Disclosure, Item38957, September 1996.

The invention therefore also pertains to a color photographic materialcomprising a compound of the formula I, and to the use of a compound ofthe formula I as an additive in a color photographic material.

The invention also pertains to a process for preventing migration of theoxidized developer in a color photographic material from one colorsensitive layer to another by incorporating a compound of the formula Iinto said material.

The compounds of the formula I of present invention are of specialadvantage when incorporated into photographic materials containingmagenta couplers of the pyrazolotriazole class.

Examples for especially suitable yellow, magenta and cyan couplers to beused in combination with compounds of the present invention are as givenin U.S. Pat. No. 5,538,840, column 33, line 3, until column 73, line 34,and publications cited therein. These passages are hereby incorporatedby reference.

The compounds of the formula I which can be used in the context of thisinvention can be incorporated into the color photographic recordingmaterial, on their own or together with the color coupler and with orwithout further additives, by pre-dissolving them in high-boilingorganic solvents. Preference is given to the use of solvents which boilat higher than 160° C. Typical examples of these solvents are the estersof phthalic acid, phosphoric acid, citric acid, benzoic acid or of fattyadds, and also alkylamides and phenols.

Further details on the structure of the color photographic material ofthe invention, and the components or further additives which can beemployed in the novel material, can be found, inter alia, in U.S. Pat.No. 5,538,840, column 27, line 25, to column 33, line 2; and further inU.S. Pat. No. 5,538,840 from column 74, line 18, to column 106, line 16;and in U.S. Pat. No. 5,780,625, column 12, line 6, until column 57, line6, and the publications cited in these 2 references; these passages ofU.S. Pat. No. 5,538,840 and U.S. Pat. No. 5,780,625 are herebyincorporated by reference. Other useful information, how compounds ofthe formula I can be used in photographic material, can be taken fromEP-A-0 871 066, page 10, line 10, until page 11, line 32, especially thereferences cited therein.

The photographic layers in the material of this invention may alsoinclude UV absorbers, which screen out the UV light and thereforeprotect the dyes, the couplers or other components againstphotodegradation. Hydroquinone compounds according to this invention maybe contained in those layers where UV absorbers are present.

UV absorbers preferably to be used in the novel material or within theprocess of present invention include benzotriazoles,2-hydroxybenzophenones, oxanilides, cyanoacrylates, salicylic esters,acrylonitrile derivatives, thiazolines and 2-hydroxyphenyltriazines.

GB-A-2,319,523 describes from page 49, line 21, until page 73, line 2,further details of the color photographic material, especially couplers(page 52, line 1, until page 56, line 22), UV absorbers (page 56, line25, until page 68, line 1) and dark stabilizers (page 68, line 2, untilpage 73, line 2). Preferred UV absorbers of the 2-hydroxyphenyltriazineclass are also described in detail, for example, in U.S. Pat. No.5,668,200, column 1, line 30, until column 7, line 55, and as specificexamples from column 26, line 31, until column 32, last line, and,together with some advantageous UV absorbers of the benzotriazole class,in U.S. Pat. No. 5,300,414, column 2 to column 10, line 54. Thesesections of U.S. Pat. No. 5,668,200 and U.S. Pat. No. 5,300,414 arehereby incorporated by reference.

The compounds of formula I may be used in combination with any known Doxscavengers such as hydrazines, hydrazides, hydroquinones of e.g. formulaHQ-1 or HQ-2; 6-hydroxychromanes of e.g. formula A-3, or hydroxylaminesof e.g. formula A-4

As silver halide emulsions it is possible to use customary silverchloride, silver bromide or silver iodide emulsions or mixtures thereof,such as silver chlorobromide and silver chloroiodide emulsions, in whichthe silver halides may have all known crystal forms. The use of silverchloride emulsions is accorded particular importance in the material ofthis novel process. The preparation of such emulsions and theirsensitization are described in Research Disclosure, Item 307105,November 1989.

The compounds of the formula I may preferably also be used asstabilizers for ethylenically unsaturated resins against prematurepolymerization or crosslinking of the resins during transport orstorage.

Preferred ethylenically unsaturated resins are for example liquid orresin-like monomers, oligomers, co-oligomers, polymers of copolymers ormixtures thereof, which possess at least one ethylenically unsaturatedbond and which are photo-polymerisable or curable with UV light.

The following Examples illustrate the invention further. Parts orpercentages relate to weight.

EXAMPLE 1 Preparation of5,7-di-tert-butyl-3-(4-trifluoromethyl-phenyl)-3H-benzofuran-2-one(compound (101), Table 1)

a) Preparation of2,4-di-tert-butyl-6-[piperidin-1-yl-(4-trifluoromethyl-phenyl)-methyl]-phenol(compound (201), Table 2).

8.29 g (97.33 mmol) of piperidine are added, at room temperature, to asolution of 7.74 g (44.43 mmol) of trifluoromethylbenzaldehyde in 50 mlof toluene. The slightly yellow-colored solution is boiled under refluxfor 4 hours; approximately 1 ml of water is separated off using a waterseparator, and a solution of 8.73 g (42.32 mmol) of2,4-di-tert-butylphenol in 15 ml of toluene is then added dropwise. Thereaction mixture is boiled at reflux for further 17 hours and thencooled to room temperature; the solvent is distilled off using a vacuumrotary evaporator. Crystallisation of the residue fromiso-propanol/methanol (1:1) yields 15.04 g (79%) of compound (201)(Table 2), m.p. 150-152° C. Molecular weight C₂₇H₃₆F₃NO (447.59).Analysis, calculated: C 72.45; H 8.11; N 3.13%. Analysis, found: C72.63; H 8.05; N 3.05%. ¹HNMR (300 MHz, CDCl₃, ppm): 1.12 (s, 9H); 1.39(s, 9H); 1.56 (m, 4H); 2.28 (bm, 6H); 4.37 (s, 1H); 6.65 (d, 1H); 7.08(d, 1H); 7.47 (m, 4H).

Compounds (202), (203) and (204) (Table 2) are obtained in analogy toExample 1a using 3-trifluoromethylbenzaldehyde [for (202)],2-trifluoromethylbenzaldehyde [for (203)] and3,5-di-trifluoromethylbenzaldehyde [for (204)] instead of4-trifluoromethylbenzaldehyde.

b) Preparation of5,7-di-tert-butyl-3-(4-trifluoromethyl-phenyl)-3H-benzofuran-2-one(compound (101), Table 1).

A solution of 12.53 g (28.0 mmol) of compound (201), prepared accordingto Example 1a, in 150 ml of dry toluene is degassed using argon and then33.6 mg (0.057 mmol) ofdichloro-[1,3bis(diphenylphosphino)propane]palladium(II) and 4.22 ml(112 mmol) of formic acid are added. The autoclave is flushed withcarbon monoxide and sealed, and a carbon monoxide pressure of 6 bar isthen applied. The reaction mixture is maintained at 140° C. for 14hours. After cooling to room temperature, the reaction mixture is pouredinto water and extracted three times using ethyl acetate. The organicphases are combined, dried over sodium sulfate and concentrated using avacuum rotary evaporator. Filtration of the residue on silica gel usingethyl acetate and crystallisation of the pure fractions from methanolyields 9.46 g (87%) of compound (101) (Table 1), m.p. 127-128° C.Molecular weight C₂₃H₂₅F₃O₂ (390.45). Analysis, calculated: C 70.75; H6.45%. Analysis, found: C 70.96; H 6.53%. ¹HNMR (300 MHz, CDCl₃, ppm):1.23 (s, 9H); 1.37 (s, 9H); 4.83 (s, 1H); 6.97 (m, 1H); 7.31 (m, 3H);7.57 (d, 2H).

Compounds (102), (103) and (104) (Table 1) are obtained in analogy toExample 1b using compounds (202), (203) and (204) (Table 2) instead ofcompound (201).

EXAMPLE 2 Preparation of5,7-di-tert-butyl-3-(4-fluorophenyl)-3H-benzofuran-2-one (compound(105), Table 1)

a) Preparation of2,4-di-tert-butyl-6-[(4-fluorophenyl)-piperidin-1-yl-methyl]-phenol(compound (205), Table 2).

8.29 g (97.33 mmol) of piperidine are added, at room temperature, to asolution of 5.52 g (44.43 mmol) of 4-fluorobenzaldehyde in 50 ml oftoluene. The slightly yellow-colored solution is boiled under reflux for16 hours; approximately 1 ml of water is separated off using a waterseparator, and a solution of 8.73 g (42.32 mmol) of2,4-di-tert-butylphenol in 15 ml of toluene is then added dropwise. Thereaction mixture is boiled at reflux for further 16 hours and thencooled to room temperature; the solvent is distilled off using a vacuumrotary evaporator. Crystallisation of the residue fromiso-propanol/methanol (1:1) yields 15.40 g (91%) of compound (205)(Table 2), m.p. 135-136° C. Molecular weight C₂₆H₃₆FNO (397.58).Analysis, calculated: C 78.55; H 9.13; N 3.52%. Analysis, found: C78.48; H 9.09; N 3.50%. ¹HNMR (300 MHz, CDCl₃, ppm): 1.12 (s, 9H); 1.37(s, 9H); 1.57 (m, 4H); 2.28 (bm, 6H); 4.35 (s, 1H); 6.63 (d, 1H); 6.91(dt, 2H); 7.08 (d, 1H); 7.32 (bm, 4H).

b) Preparation of5,7-di-tert-butyl-3-(4-fluorophenyl)-3H-benzofuran-2-one (compound(105), Table 1).

A solution of 11.13 g (28.0 mmol) of compound (205), prepared accordingto Example 2a, in 150 ml of dry toluene is degassed using argon and then33.6 mg (0.057 mmol) ofdichloro-[1,3-bis(diphenylphosphino)propane]palladium(II) and 4.22 ml(112 mmol) of formic acid are added. The autoclave is flushed withcarbon monoxide and sealed, and a carbon monoxide pressure of 6 bar isthen applied. The reaction mixture is maintained at 140° C. for 14hours. After cooling to room temperature, the reaction mixture is pouredinto water and extracted three times using ethyl acetate. The organicphases are combined, dried over sodium sulfate and concentrated using avacuum rotary evaporator. Filtration of the residue on silica gel usingethyl acetate and crystallisation of the pure fractions from methanolyields 8.53 g (90%) of compound (105) (Table 1), m.p. 146-147° C.Molecular weight C₂₂H₂₅FO₂ (340.44). Analysis, calculated: C 77.62; H7.40%. Analysis, found: C 77.66; H 7.35%. ¹HNMR (300 MHz, CDCl₃, ppm):1.22 (s, 9H); 1.36 (s, 9H); 4.74 (s, 1H); 6.99 (m, 3H); 7.16 (m, 2H);7.26 (d, 1H).

EXAMPLE 3 Preparation of5,7-di-tert-butyl-3-(4-cyanophenyl)-3H-benzofuran-2-one (compound (106),Table 1)

a) Preparation of2,4-di-tert-butyl-6-[(4-cyanophenyl)-piperidin-1-yl-methyl]-phenol(compound (206), Table 2).

8.29 g (97.33 mmol) of piperidine are added, at room temperature, to asolution of 5.83 g (44.43 mmol) of 4-cyanobenzaldehyde in 50 ml oftoluene. The slightly yellow-colored solution is boiled under reflux for4 hours; approximately 1 ml of water is separated off using a waterseparator, and a solution of 8.73 g (42.32 mmol) of2,4-di-tert-butylphenol in 15 ml of toluene is then added dropwise. Thereaction mixture is boiled at reflux for further 6 hours and then cooledto room temperature; the solvent is distilled off using a vacuum rotaryevaporator. Crystallisation of the residue from methanol yields 12.95 g(75%) of compound (206) (Table 2), m.p. 165-166° C. Molecular weightC₂₇H₃₆N₂O (404.60). Analysis, calculated: C 80.15; H 8.97; N 6.92%.Analysis, found: C 80.01; H 9.00; N 6.78%. ¹HNMR (300 MHz, CDCl₃, ppm):1.12 (s, 9H); 1.36 (s, 9H); 1.57 (m, 4H); 2.28 (bm, 6H); 4.34 (s, 1H);6.63 (d, 1H); 7.09 (d, 1H); 7.51 (m, 4H).

Compounds (207) and (208) (Table 2) are obtained in analogy to Example3a using 3-cyanobenzaldehyde [for (207)] and 3,5-dicyanobenzaldehyde[for (208)] instead of 4-cyanobenzaldehyde.

b) Preparation of5,7-di-tert-butyl-3-(4-cyanophenyl)-3H-benzofuran-2-one (compound (106),Table 1).

A solution of 11.33 g (28.0 mmol) of compound (206), prepared accordingto Example 3a, in 150 ml of dry toluene is degassed using argon and then33.6 mg (0.057 mmol) ofdichloro-[1,3-bis(diphenylphosphino)propane]palladium(II) and 4.22 ml(112 mmol) of formic acid are added. The autoclave is flushed withcarbon monoxide and sealed, and a carbon monoxide pressure of 6 bar isthen applied. The reaction mixture is maintained at 140° C. for 14hours. After cooling to room temperature, the reaction mixture is pouredinto water and extracted three times using ethyl acetate. The organicphases are combined, dried over sodium sulfate and concentrated using avacuum rotary evaporator. Filtration of the residue on silica gel usingethyl acetate and crystallisation of the pure fractions from methanolyields 7.72 g (79%) of compound (106) (Table 1), m.p. 136-137° C.Molecular weight C₂₃H₂₅NO₂ (347.46). Analysis, calculated: C 79.51; H7.25; N 4.03%. Analysis, found: C 79.36; H 6.98; N 3.82%. ¹HNMR (300MHz, CDCl₃, ppm): 1.23 (s, 9H); 1.36 (s, 9H); 4.83 (s, 1H); 6.95 (m,1H); 7.31 (m, 3H); 7.61 (d, 2H).

Compounds (107) and (108) (Table 1) are obtained in analogy to Example3b using compounds (207) and (208) (Table 2) instead of compound (206).

EXAMPLE 4 Preparation of5,7-di-tert-butyl-3-(4-methoxycarbonylphenyl)-3H-benzofuran-2-one(compound (109), Table 1)

a) Preparation of2,4-di-tert-butyl-6-[4-methoxcarbonylphenyl)-piperidin-1-yl-methyl]-phenol(compound (209), Table 2).

18.98 g (222.94 mmol) of piperidine are added, at room temperature, to asolution of 16.71 g (101.78 mmol) of 4-methoxycarbonylbenzaldehyde in100 ml of toluene. The slightly yellow-colored solution is boiled underreflux for 15 hours; approximately 2 ml of water is separated off usinga water separator, and a solution of 20.0 g (96.93 mmol) of2,4-di-tert-butylphenol in 30 ml of toluene is then added dropwise. Thereaction mixture is boiled at reflux for 1 hour and then cooled to roomtemperature; the solvent is distilled off using a vacuum rotaryevaporator. Crystallisation of the residue from iso-propanol yields32.12 g (75%) of compound (209) (Table 2), m.p. 167-168° C. Molecularweight C₂₈H₃₉NO₃ (437.63). Analysis, calculated: C 76.85; H 8.98; N3.20%. Analysis, found: C 76.68; H 8.84; N 3.01%. ¹HNMR (300 MHz, CDCl₃,ppm): 1.11 (s, 9H); 1.37 (s, 9H); 1.56 (m, 4H); 2.30 (bm, 6H); 3.82 (s,3H); 4.40 (s, 1H) 6.64 (d, 1H); 7.08 (d, 1H); 7.45 (bd, 2H); 7.90 (dd,2H).

b) Preparation of5,7-di-tert-butyl-3-(4-methoxycarbonylphenyl)-3H-benzofuran-2-one(compound (109), Table 1).

A solution of 10.50 g (24.0 mmol) of compound (209), prepared accordingto Example 4a, in 120 ml of dry toluene is degassed using argon and then28.8 mg (0.048 mmol) ofdichloro-[1,3-bis(diphenylphosphino)propane]palladium(II) and 3.62 ml(96 mmol) of formic acid are added. The autoclave is flushed with carbonmonoxide and sealed, and a carbon monoxide pressure of 6 bar is thenapplied. The reaction mixture is maintained at 140° C. for 14 hours.After cooling to room temperature, the reaction mixture is poured intowater and extracted three times using ethyl acetate. The organic phasesare combined, dried over sodium sulfate and concentrated using a vacuumrotary evaporator. Filtration of the residue on silica gel using ethylacetate and crystallisation of the pure fractions from methanol yields7.41 g (81%) of compound (109) (Table 1), m.p. 135-1360C. Molecularweight C₂₄H₂₈O₄ (380.49). Analysis, calculated: C 75.76; H 7.42%.Analysis, found: C 75.67; H 7.28%. ¹HNMR (300 MHz, CDCl₃, ppm): 1.22 (s,9H); 1.37 (s, 9H); 3.85 (s, 3H); 4.74 (s, 1H); 6.96 (m, 1H); 7.26 (m,3H); 7.98 (d, 2H).

EXAMPLE 5 Preparation of5,7-di-tert-butyl-3-(4-n-octyloxycarbonylphenyl)-3H-benzofuran-2-one(compound (110), Table 1)

A suspension of 14.0 g (36.80 mmol) of compound (109), preparedaccording to Example 4b, 23.26 ml (147.2 mmol) of 1-octanol and 92 mg(0.368 mmol) of dibutyltinoxide (Bu₂SnO) is heated at 170° C. for 2hours, whereas an orange solution is formed. Methanol is continuouslydistilled off the reaction mixture. After cooling to room temperature,the crude reaction mixture is treated with a 50 ml of a 1:19 mixture ofethyl acetate/hexane 1:1 and filtered through a pad of silica. Removalof the solvent using a vacuum rotary evaporator yields 17.53 g (99%) ofcompound (110) (Table 1), as a pale yellow oil. ¹HNMR (300 MHz, CDCl₃,ppm): 0.90 (t, 3H); 1.35 (s, 9H); 1.38 (bs, 10H); 1.46 (s, 9H); 1.78 (q,2H); 4.33 (t, 3H); 4.92 (s, 1H); 7.05 (s, 1H); 7.35 (d, 2H); 7.36 (s,1H); 8.07 (d, 2H).

Compounds (111), (112), (113), (114), (115), (116) and (117) (Table 1)are obtained in analogy to Example 5 using 1-dodecanol, 1-octadecanol,1-nonadecanol, 1-docosanol, 2-ethylhexanol, 1,6-hexanediol and1,12-dodecanediol instead of 1-octanol. For the preparation of compounds(116) and (117) only half of an equivalent of 1,6-hexanediol and1,12-dodecanediol in respect to the compound (109) was used.

TABLE 1 no. compound 101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

TABLE 2 no. compound 201

202

203

204

205

206

207

208

209

EXAMPLE 6 Prevention of Migration of the Oxidized Developer in a ColorPhotographic Material

To evaluate compounds of this invention with respect to their ability asinterlayer scavengers for oxidized developing agent, three layerphotographic test elements are prepared by providing layers in the orderindicated on a polyethylene-coated paper support:

Test Element 1 (Reference Sample)

(1) A photosensitive layer containing:

260 mg.m⁻² (based on silver) of an unsensitized silver bromide emulsion.

1875 mg.m⁻² of gelatin.

250 mg.m⁻² of magenta-dye-forming coupler M-2

250 mg.m⁻² of tricresylphosphate.

2-sulfonate-4,8-diisobutyl-naphtatene, sodium salt surface active agent.

7-methyl-5-hydroxy-1,3,8-triazaindolizine antifoggant.

(2) An interlayer containing:

1800 mg.m⁻² of gelatin.

300 mg.m⁻² of tricresylphosphate.

2-sulfonate-4,8-diisobutyl-naphtalene, sodium salt surface active agent.

(3) A layer containing:

1800 mg.m⁻² of gelatin.

180 mg.m⁻² of dibutylphthalate.

2-sulfonate-4,8-diisobutyl-naphtalene, sodium salt surface active agent.

2-hydroxy-4,6-dichloro-1,3,5-triazine, potassium salt hardener.

Test Element 2 (Control Sample)

(1) A photosensitive layer having the same composition as thephotosensitive layer of test element 1.

(2) An interlayer having the same composition as the interlayer of testelement 1.

(3) A layer containing:

1800 mg.m⁻² of gelatin.

272 mg.m⁻² of cyan-dye-forming coupler C₂

180 mg.m⁻² of dibutylphthalate.

2-sulfonate-4,8-diisobutyl-naphtalene, sodium salt surface active agent.

2-hydroxy-4,6-dichloro-1,3,5-triazine, potassium salt hardener.

Test Elements 3 and 4

(1) A photosensitive layer having the same composition as thephotosensitive layer of test element 1.

(2) An interlayer containing:

1800 mg.m⁻² of gelatin.

20 mg.m⁻² of oxidized developer scavenger as indicated in Table 3 below

300 mg.m⁻² of tricresylphosphate.

2-sulfonate-4,8-diisobutyl-naphtalene, sodium salt surface active agent.

(3) A layer having the same composition as the top layer of test element2.

The test elements are imagewise exposed through a step wedge withdensity increment 0.15 and thereafter subjected to the AGFA P-94developing process.

Upon processing of the test elements, some oxidized developer is proneto migrate from the layer in which it is formed, for example theundermost, magenta-dye-providing layer, to the topmost layer containingthe cyan-dye-forming coupler, thereby producing unwanted cyan dye. Theamount of cyan dye that is generated depends on the ability of theinterlayer to prevent the diffusion of oxidized developer. The cyandensity at the exposure amount giving a magenta density of 1.5 isreported in Table 3. Any cyan density inferior to that observed for testelement 2 indicates scavenging of the oxidized developer.

TABLE 3 Test Interlayer Cyan density at a magenta element scavengerdensity of 1.5 1 (reference) — 0.239 2 (control) — 0.293 3 Compound(109) 0.254 4 Compound (101) 0.253

It is clear from the data in Table 3 that compounds within the scope ofthis invention are quite effective in preventing the oxidized developerfrom wandering and forming dye in the wrong layer.

EXAMPLE 7 Stabilization of Multiple-extruded Polypropylene

1.3 kg of polypropylene powder (Profax 6501), which has beenprestabilized with 0.025% of Irganox®1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) (melt index 3.2 g/10min, measured at 230° C./2.16 kg) are blended with 0.05% of Irganox®1010(pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 0.05% ofcalcium stearate, 0.03% of DHT 4A® (Kyowa Chemical Industry Co., Ltd.,[Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O]) and 0.05% of compound of Table 4. Thisblend is then extruded in an extruder having a cylinder diameter of 20mm and a length of 400 mm at 100 rpm, the 3 heating zones being adjustedto the following temperatures: 260, 270, 280° C. The extrudate is cooledby drawing it through a water bath and is then granulated. Thisgranulate is repeatedly extruded. After 3 extrusions, the melt index ismeasured (at 230° C./2.16 kg). A substantial increase in the melt indexdenotes pronounced chain degradation, i.e. poor stabilization. Theresults are summarized in Table 4.

TABLE 4 Compound of Melt index after 3 Table 1 extrusions — 17.5 101 4.7105 4.7 106 4.7 109 4.8 110 4.7

EXAMPLE 8 Stabilization of Polyethylene During Processing

100 parts of polyethylene powder (Lupolen®5260 Z) are blended with 0.05part of Irganox®1010 (pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) and 0.05 partof a compound of Table 5 and the blend is kneaded in a Brabenderplastograph at 220° C. and 50 rpm. During this time the kneadingresistance is recorded continuously as torque. In the course of thekneading time the polymer begins to crosslink after prolonged constancy,as can be determined by the rapid increase in torque. The time takenuntil a marked increase in torque is shown in Table 5 as a measure ofthe stabilizing action. The longer this time is the better thestabilizing action.

TABLE 5 Compound of Time until increase Table 1 in torque (min) — 9.7101 27.5 105 27.0 106 27.5 109 27.5 110 27.5

EXAMPLE 9 Stabilization of Multiple-extruded Polypropylene at HighTemperature

1.5 kg of polypropylene powder (Profax 6501), which has beenprestabilized with 0.008% of Irganox®1076 (n-octadecyl3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) (melt index 3.2 g/10min, measured at 230° C./2.16 kg) are blended with 0.05% of Irganox®1010(pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 0.10% ofcalcium stearate and 0.015 to 0.100% of stabilizer or stabilizer mixtureaccording to Table 6. This blend is then extruded in an extruder havinga cylinder diameter of 20 mm and a length of 400 mm at 100 rpm, the 3heating zones being adjusted to the following temperatures: 280, 320,340° C. The extrudate is cooled by drawing it through a water bath andis then granulated. This granulate is repeatedly extruded. After 5extrusions, the melt index is measured (at 230° C./2.16 kg). Asubstantial increase in the melt index denotes pronounced chaindegradation, i.e. poor stabilization. The results are summarized inTable 6.

TABLE 6 Melt index after Concentration in 5 extrusions Stabilizers % (byweight) 280° C. 320° C. 340° C. Irgafos ®168^(a) 0.100 9.7 43.8 80.1Sandostab ®P-EPQ^(b) 0.050 6.3 23.9 61.5 Compound (101) 0.015 8.5 19.622.5 Irgafos ®168^(a) 0.045 7.2 24.2 26.5 Compound (101) 0.005Sandostab ®P-EPQ^(b) 0.045 5.7 15.9 24.7 Compound (101) 0.005 Forfootnotes ^(a) and ^(b) see the end of Table 25.

EXAMPLE 10 Preparation of Polyether/polyurethane Soft Foams as Well asthe Stabilization Thereof

Exactly 470 mg (0.3%, based on the polyol) of a stabilizer mixture ofthis invention is dissolved in 157 g of an antioxidant-freepolyether/polyol, Lupranol®2045 (trifunctional polyether/polyol havingprimary hydroxyl groups; hydroxyl number 35 mg KOH/g, water content lessthan 0.1%, acid number less than 0.1 mg KOH/g). 10.24 g of a solutionconsisting of 1.74 g Tecostab® (polysilicone supplied by Goldschmidt,Germany], 0.48 g diazabicyclooctane (amine catalyst) and 0.8 g of waterare added and the reaction mixture is stirred vigorously for 60 secondsat 100 rpm. 3.2 g of a solution of 0.32 g of tin octoate (catalyst) in2.9 g of the above polyol is added and the reaction mixture is againstirred vigorously for 60 seconds at 100 rpm. With vigorous stirring, 98g of an isocyanate (Lupranat®T80, supplied by BASF; toluylene-2,4- andtoluylene-2,6-diisocyanate mixture) are then added immediately and after6 seconds the mixture is poured into a lined mould and the exothermictemperature is measured during foaming to a foam block. The foam blocksare cooled for 24 hours in a climatic chamber at 5° C. and stored. 2 cmslices are sawed from the center of the blocks and round (cylindrical)test samples are cut therefrom using a boring tool. The samples are agedin a test tube in the presence of air at room temperature and 200° C.for 30 minutes in a pre-heated alu-block thermostat (dynamic heat test).The yellowing of these test samples is determined as Yellowness Index(YI) according to ASTM 1925-77. Low YI values denote littlediscoloration, high YI values severe discoloration of the samples. Theresults are summarized in Tables 7 and 8.

TABLE 7 Concentration of stabilizers YI YI Example in % (by weight) roomtemp. 200° C. 10a^(i) — 1.0 70.0 10b^(k) 0.15% Compound (101) −1.1 2.00.15% Irganox ®5057^(c) 10c^(k) 0.15% Compound (102) −0.9 1.8 0.15%Irganox ®5057^(c) 10d^(k) 0.15% Compound (104) −1.3 2.0 0.15%Irganox ®5057^(c)

TABLE 8 Concentration of stabilizers YI YI Example in % (by weight) roomtemp. 200° C. 10e^(i) — 0.5 69.0 10f^(k) 0.10% Compound (101) −1.1 2.10.10% Irganox ®5057^(c) 0.10% Irganox ®1135^(d) 10g^(k) 0.10% Compound(102) −0.9 1.9 0.10% Irganox ®5057^(c) 0.10% Irganox ®1135^(d) 10h^(k)0.10% Compound (104) −1.3 2.0 0.10% Irganox ®5057^(c) 0.10%Irganox ®1135^(d)

For footnotes c), d), i) and k) see the end of Table 25.

EXAMPLE 11 Stabilizing Polypropylene Fibers Processed at 300° C.

2.0 kg of polypropylene powder (B 10 FB® from Polychim S.A., France),which has a melt index of 12.0 g/dmin measured in accordance with DIN53735 at 230° C. under 2.16 kg, is homogenized with 0.05% of calciumstearate and with the stabilizers indicated in Tables 9 and 10 for 2minutes in a high-speed mixer. This mixture is extruded at 60revolutions per minute in an extruder having a barrel diameter of 20 mmand a length of 400 mm, the three heating zones being set at thefollowing temperatures: 200, 220 and 220° C. The extrudate is passedthrough a water bath for cooling and then granulated. These granules areprocessed to give a multifilament fiber. This is done using asingle-screw extruder with a melt pump and a 37-hole spinning head. Themaximum processing temperature is 300° C.

A portion of the unstretched fiber thus obtained is pressed for 6minutes at 230° C. to form a sheet with a thickness of 2 mm. The meltindex (MFI, melt flow index) of this sheet is measured in accordancewith DIN 53735 at 230° C. and 2.16 kg. A large increase in the meltindex denotes severe chain degradation and thus poor stabilization. Theresults are compiled in Table 9.

Another portion of the unstretched fiber thus obtained is treated with alubricant (Limanol®P 25, Schill und Seilacher, Böblingen, Germany) andsubjected to preliminary drawing. This preliminary drawing leads to afiber strand having a linear density of 416 g/90 m. This means that afiber strand 90 m in length has a weight of 416 g. In a furtheroperation, this fiber strand is again drawn at 120° C. by a factor of3.2 using a drawing apparatus. This leads to a fiber strand having alinear density of 130 g/90 m.

A portion of this fiber strand is used to produce a knitted tube. Theyellowness index (YI₁) of this knitted tube is determined in accordancewith ASTM D 1925-77. Low YI₁ values denote little discoloration, highYI₁ values severe discoloration of the samples. The results are compiledin Table 9. This knitted tube is exposed in the presence of from 4 to 6ppm nitrogen dioxide (NO₂) at 40° C. and 87% relative atmospherichumidity for 48 hours in accordance with AATCC 164. The yellowness index(YI2) of this exposed knitted tube is determined in accordance with ASTMD 1925-77. Low YI₂ values denote little discoloration, high YI₂ valuessevere discoloration of the samples. The results are compiled in Table9.

Another portion of the fiber strand is used to carry out an oven ageingtest at 100° C. In this test a measurement is made, in days, of the timetaken for the fiber strand to tear under the test conditions. The longerthe period before tearing of the fiber strand, the better thestabilization. The results are compiled in Table 10.

Another portion of the unstretched fiber is pressed for 6 minutes at230° C. to form a thin film with a thickness of 0.10 mm. This film issubjected to a Xenon test in accordance with DIN 53387. In this test,the film is exposed in a Xenon 1200 weathering apparatus until acarbonyl index of 0.25 is observed in the wavelength range from 1760 to1680 cm⁻¹. The larger the number, the better the stabilization. Theresults are compiled in Table 10.

TABLE 9 YI₁ YI₂ after after MFI Exam- spin- NO₂ after ple Stabilizersning exposure spinning 11a^(i) — 0.3 1.2 110.0 11b^(k) 0.100% Compound(106) 1.3 4.5 34.3 0.050% Tinuvin ®622^(e) 11c^(k) 0.100% Compound (106)1.5 5.3 32.5 0.050% Chimassorb ®944^(f) 11d^(k) 0.100% Compound (106)0.6 4.2 31.8 0.050% Chimassorb ®119^(g) 11e^(k) 0.075% Compound (106)0.6 4.6 32.3 0.050% Tinuvin ®622^(e) 0.075% Irgafos ®168^(a) 11f^(k)0.075% Compound (106) 1.4 5.9 33.5 0.050% Chimassorb ®944^(f) 0.075%Irgafos ®168^(a) 11g^(k) 0.075% Compound (106) 1.6 4.6 31.6 0.050%Chimassorb ®944^(f) 0.075% Irgafos ®38^(h) 11h^(k) 0.075% Compound (106)1.5 4.7 32.5 0.050% Chimassorb ®119^(g) 0.075% Irgafos ®168^(a) Forfootnotes ^(a), ^(e), ^(f), ^(g), ^(h), ^(i) and ^(k) see the end ofTable 25.

TABLE 10 Oven ageing Xenon test Example Stabilizers (days) (hours)11a^(i) —  1  195 11c^(k) 0100% Compound (106) 38 1345 0.050%Chimassorb ®944^(f) 11d^(k) 0.100% Compound (106) 37 1580 0.050%Chimassorb ®119^(g) 11f^(k) 0.075% Compound (106) 39 1320 0.050%Chimassorb ®944^(f) 0.075% Irgafos ®168^(a) 11g^(k) 0.075% Compound(106) 39 1325 0.050% Chimassorb ®944^(f) 0.075% Irgafos ®38^(h) 11h^(k)0.075% Compound (106) 38 1610 0.050% Chimassorb ®119^(g) 0.075%Irgafos ®168^(a) For footnotes ^(a), ^(f), ^(g), ^(h), ^(i) and ^(k) seethe end of Table 25.

EXAMPLE 12 Preparation of Polyolefin Hollow Articles by the RotomoldingProcess

100 Parts of low density polyethylene, copolymerized with hexene(PE-LLD), type Quantum® Petrothene® GA-635-661, having a melt flow indexof 6.5 g/10 min and a density of 0.935 g/cm³, are mixed with 0.170 partof Chimassorb® 944 [formula see footnote (b) after Table 10], 0.050 partof zinc stearate and the stabilizers cited in Tables 11 and 12 at 232°C. in a Superior/MPM Extruder, fitted with a 24:1 Maddock type L/Dscrew, at 100 revolutions per minute. The polymer is then ground. Theparticle size of the polymer is from 150 to 500 μm. Owing to the largersurface of the particles obtained by grinding, the heat can be absorbedfaster, which goes hand in hand with a lower energy consumption.

The actual rotomolding process or rotational molding process, whichpermits the production of fairly large three-dimensional solids, iscarried out in a Clamshell type rotomolder FSP M20. In this machine, analuminium mold, which is mounted on an arm and into which the plasticsample is filled, is heated with a gas burner with circulation of thehot air over 5 minutes to 316° C., or over 6 minutes to 329° C., and isthen kept at this temperature for a specific time (see Tables 11 and12). Subsequently, the oven is opened and the mold is cooled first for 7minutes with circulating air, then for 7 minutes by spraying with waterand finally for another 2 minutes with circulating air. During theentire heating and cooling process, the mold, which is mounted on twoaxes at right angles to each other, is rotated, the speed of the mainaxis being kept at 6 revolutions per minute and the rotational ratiobeing 4.5:1. After cooling, the lid of the mold is opened and theresultant hollow article is taken out. The yellowness index (YI) of theexterior of the molded articles is determined according to ASTM D1925-70. Low YI values denote little discoloration, high YI valuesstrong discoloration of the samples. The less discoloration, the moreeffective the stabilizer. The results are summarized in Tables 11 and12.

TABLE 11 Rotomolding at 316° C. Yellowness Index after ExamplesStabilizer 8 minutes 10 minutes Example 12a^(i) 0.05% Irganox ® 1010^(l)6.2 17.7 0.10% Irgafos ®168^(a) Example 12b^(k) 0.02% compound (107) 4.2 5.2 0.08% Irgafos ®168^(a)

TABLE 12 Rotomolding at 329° C. Yellowness Index after ExamplesStabilizer 6 minutes 8 minutes Example 12c^(i) 0.05% Irganox ® 1010^(l)3.9 16.5 0.10% Irgafos ®168^(a) Example 12d^(k) 0.02% compound (107) 4.1 5.6 0.08% Irgafos ®168^(a) For footnotes ^(a), ^(i), ^(k) and ^(l) seethe end of Table 25.

EXAMPLE 13 Stabilisation of Polyethylene which is in Permanent Contactwith Water

0.10% by weight of calcium stearate and a stabilizer mixture comprising0.10% by weight of Irganox®1010 (pentaerythritoltetrakis[3-(3,5di-tert-butyl-4-hydroxyphenyl)propionate]), 0.05% byweight of Irgafos®168 (tris(2,4-di-tert-butylphenyl)phosphite) and 0.05%by weight of compound (104) (Table 1) is added dry to a polyethylenepolymer (Hostalene® CRP 100; PE-HD) taken direct from a reactor and areincorporated therein in a Pappenmaier mixer (type 20) within 2 minutes.

In an extruder, of Schwabenthan, the stabilized polyethylene ishomogenised and processed to granulate. For the extraction tests inwater, 200 mm by 150 mm by 2 mm test plates are pressed from thegranulate of the individual formulations using a table press. To easethe demoulding of the test plates, the pressing process is carried outbetween two aluminium foils.

The stabilizer extraction tests are carried out with deionised water.Preliminary heating of the extraction vessels is carried out in acirculating air oven, of Heraeus (Hanau, Germany), at a maximumtemperature deviation of 1.5° C. Glass vessels are used for extractiontests below the boiling point of water, such as at 80° C. Owing to therisk of oversaturating the water with stabilizers, the amount of liquidused for the tests is fixed at c. 400 ml per c. 70 g of polymer and thewater is replaced with fresh water at regular intervals, i.e. whenever asample is taken.

The test plates are subjected to the above test conditions for 50 daysat 80° C. Upon termination of the extraction test, the residualstabilizer content and the oxidation induction time of the test platesare determined.

The residual content of sterically hindered phenol, Irganox®1010, isdetermined using an internal standard in an HPLC appliance of theSpectra Physics SP 8800 type, equipped with autosampler and UV/VISdetector of the Spectra 200 type. The chromatography is carried out atroom temperature using a Hyperchrome 125×4.6 mm type column which isfilled with Nucleosil C 185 μm. The injection volume is 14 μl at a flowrate of 1.5 ml/minute. UV detection takes place at 270 nm.

The oxidation induction time which is determined using a“DuPont-Instrument 910 Differential Scanning Calorimeter”, of TAInstruments (Alzenau, Germany), and taking a 5 to 10 mg amount ofsample, describes the time in minutes at constant thermal stress (190°C./O₂) up to the start of the complete degradation of the polyethylenesample. The longer the oxidation induction time, the better stabilizedthe polyethylene and the more stable is the polyethylene againstextracting water with which it is in permanent contact. The results showthat the stability of polyolefins which are in permanent contact withextracting media is improved if they contain a compound of the formula Iaccording to the instant invention as stabilizer.

EXAMPLE 14 Measuring the Discoloration of Powder Coatings Based on aCarboxy-functional Polyester and Cured in Electric and Gas Ovens

To prepare the powder coating composition based on a carboxy-functionalpolyester, components 1 to 6 (formulation without additives) orcomponents 1 to 7 (formulation containing the stabilizers) are employedin the sequence indicated (cf. Table 13).

TABLE 13 Examples (amount in grams) Components 1a 1b to 1i 1. Crylcoat ®360^(a) 591 591 2. Araldit ® GT 7004^(b) 394 394 3.Octadecyltrimethylammonium bromide^(c) 3.6 3.6 4. Resiflow ® PV 88^(d)12 12 5. Benzoin^(e) 3 3 6. Titanium dioxide type R-KB-5^(f) 500 500 7.Stabilizers (see Tables 14 and 15) — 6 Total: 1503.6 1509.6^(a)Crylcoat ® 360 from UCB S.A., Drogenbos, Belgium. ^(b)Araldit ® GT7004 (Ciba Specialty Chemical Inc.) is a bisphenol A diglycidyl ether.^(c)Octadecyltrimethylammonium bromide from Fluka AG, Buchs,Switzerland. ^(d)Resiflow ® PV 88 from Worlée Chemie GmbH, Lauenburg,Germany. ^(e)Benzoin from Fluka AG. ^(f)Titanium dioxide type R-KB-5from Bayer AG, Leverkusen, Germany.

The components weighed out in this way are mixed using a planetarystirrer. The mixture is then extruded on a prism extruder at 300revolutions/minute and at 100° C. and is rolled out. The powder coatingcomposition is coarsely comminuted using a bench cutter and is ground ina Retsch ZM-1 ultracentrifugal mill with a 0.75 mm annular-perforationscreen at 15,000 revolutions/minute. Finally, the powder is passedthrough a 30 μm screen on a centrifugal screening machine.

The finished powder coating composition is sprayed electrostatically toa coat thickness of 70 μm onto aluminium panels using an ESB-Wagnercorona cup gun at 60 kV. Some of the coated panels are cured at 180° C.for 90 minutes in an electric oven. The remaining coated panels arecured at 180° C. for 45 minutes in a gas oven with an NO₂ content of 20ppm. The yellowness index (YI) of the samples is determined inaccordance with ASTM D 1925-70. Low YI values denote littlediscoloration, high YI values denote severe discoloration of thesamples. The less the discoloration, the more effective the stabilizer.The results are summarized in Tables 14 and 15.

TABLE 14 Curing for 90 minutes in an electric oven at 180° C. Yellownessindex Stabilizers after 90 minutes Examples (% rel. to components 1 to5) (ASTM D 1925-70) Example 14a^(i) — 3.1 Example 14b^(k) 0.60% Compound(110) 2.7 Example 14c^(k) 0.50% Irgafos ®168^(a) 2.7 0.10% Compound(110) Example 14d^(k) 0.15% Irgafos ®168^(a) 2.7 0.15% HALS mixture^(m)0.30% Compound (110) Example 14e^(k) 0.15% Irgafos ®168^(a) 2.7 0.15%Irganox ®1010^(l) 0.30% Compound (110) For footnotes ^(a), ^(i), ^(k),^(m) and ^(i) see the end of Table 25.

TABLE 15 Curin for 45 minutes in a gas oven at 180° C. Yellowness indexStabilizers after 90 minutes Examples (% rel. to components 1 to 5)(ASTM D 1925-70) Example 14f^(i) — 4.2 Example 14g^(k) 0.60% Compound(110) 3.4 Example 14h^(k) 0.50% Irgafos ®168^(a) 3.4 0.10% Compound(110) Example 14i^(k) 0.15% Irgafos ®168^(a) 3.2 0.15% HALS mixture^(m)0.30% Compound (110) For footnotes ^(a), ^(i), ^(k) and ^(m) see the endof Table 25.

EXAMPLE 15 Stabilizing Polypropylene in the Case of Multiple Extrusionand at Especially High Temperatures

1.5 kg of polypropylene powder (Profax®6501), which has been initiallystabilized with 0.008% of Irganox®1076 (n-octadecyl3-[3,5-di-tert-butylhydroxyphenyl]propionate) (with a melt index of 3.2measured at 230° C. and under 2.16 kg), are mixed with 0.10% of calciumstearate and 0.015 to 0.20% of the stabilizers listed in Table 16. Thismixture is extruded in an extruder having a barrel diameter of 20 mm anda length of 400 mm at 100 revolutions per minute, the maximum extrudertemperature being set at 280, 300, 320 and 340° C. For cooling, theextrudate is drawn through a water bath and then granulated. Thesegranules are extruded repeatedly. After 5 extrusions, the melt index ismeasured (at 230° C. under 2.16 kg). A large increase in the melt indexdenotes severe chain breakdown and hence poor stabilization. The resultsare summarized in Table 16.

TABLE 16 Amount Melt index Example Stabilizers (% by wt.) after 5extrusions Example 15a^(i) Irgafos ®168^(a) 0.10 18.2 Irganox ®1010^(l)0.10 Chimassorb ®944^(f) 0.20 Example 15b^(k) Compound (101) 0.015  8.7Irgafos ®168^(a) 0.10 Irganox ®1010^(l) 0.05 Chimassorb ®944^(f) 0.10Example 15c^(k) Compound (101) 0.015  8.3 Irgafos ®168^(a) 0.10Irganox ®1010^(l) 0.05 Chimassorb ®119^(g) 0.10 For footnotes ^(a),^(f), ^(g), ^(i), ^(k) and ^(l) see the end of Table 25.

EXAMPLE 16 Stabilization of Polycarbonate

1.0 kg of a polycarbonate powder which has been dried for 8 hours at120° C. in a vacuum drying oven (Lexan®115, of General Electric) and 0.1to 0.6 g (0.01 to 0.06%) of the stabilizers listed in Table 17 are mixedfor 2 minutes in a Henschel mixer. This mixture is then extruded in aSchwabenthan extruder at a maximum of 280° C. The polymer string is thengranulated. Using an injection moulding machine, plates having a layerthickness of 2 mm are then moulded from the granulate so obtained at amaximum of 300° C. These plates are then aged in a circulating air ovenat 135° C. for 2000 hours. The yellowness index (YI) of these plates isthen determined according to ASTM D 1925-70 and the transmission isdetermined in percent at 450 nm. Low YI values denote littlediscoloration, high YI values high discoloration of the patterns. Theless discoloration, the more effective the stabilizer. The higher thetransmission values, the more effective the stabilizer. The results arecompiled in Tables 17 and 18.

TABLE 17 Yellowness Yellowness index index prior after 2000 hoursExample Stabilizers to oven-ageing at 135° C. 16a^(i) — 4.2 25.0 16b^(i)0.05% Irgafos ®168^(a) 3.4 23.5 16c^(k) 0.01% Compound (101) 3.4 16.416d^(k) 0.01% Compound (112) 3.5 14.3 16e^(k) 0.05% Irgafos ®168^(a) 3.215.2 0.01% compound (101) 16f^(k) 0.05% Irgafos ®168^(a) 3.1 14.3 0.01%compound (112)

TABLE 18 Transmission Transmission in % in % prior to after 2000 hoursExample Stabilizers oven-aging at 135° C. 16a^(i) — 84.7 76.4 16b^(i)0.05% Irgafos ®168^(a) 84.7 77.8 16c^(k) 0.01% Compound (101) 85.8 81.316d^(k) 0.01% Compound (112) 85.9 81.8 16e^(k) 0.05% Irgafos ®168^(a)85.7 81.3 0.01% Compound (101) 16f^(k) 0.05% Irgafos ®168^(a) 85.9 81.90.01% compound (112) For footnotes ^(a), ^(i) and ^(k) see the end ofTable 25.

EXAMPLE 17 Stabilization of Polycarbonate

1.0 kg of a polycarbonate powder which has been dried for 8 hours at120° C. in a vacuum drying oven (Lexan®145, of General Electric) ischarged with the stabilizers listed in Table 19 and is mixed for 2minutes in a Henschel mixer. This mixture is then extruded in aSchwabenthan extruder at a maximum of 280° C. The polymer string is thengranulated. Using an injection moulding machine, plates having a layerthickness of 2 mm are then moulded from the granulate so obtained at amaximum of 300° C. These plates are then aged in a circulating air ovenat 135° C., the time in hours until the yellowness index (YI) reaches avalue of 20 according to ASTM D 1925-70 being measured. The longer thetime, the more effective the stabilizer. The results are compiled inTable 19.

TABLE 19 Time in hours at Example Stabilizers 135° C. to YI = 20 17a^(i)— 1560 17b^(i) 0.05% Irgafos ®168^(a) 2000 0.008% Compound (106) 17c^(k)0.022% Irgafos ®168^(a) 2350 0.012% Irganox ®1076^(n) 17d^(k) 0.009%Compound (106) 2350 0.034% Irgafos ®168^(a) 0.017% Irganox ®1076^(n) Forfootnotes ^(a), ^(i), ^(k) and ^(n) see the end Table 25.

EXAMPLE 18 Stabilisation of Polybutylene Terephthalate (PBT)

1.0 kg of a polybutylene terephthalate powder which has been dried for10 hours at 100° C. in a vacuum drying oven (Crastin®S600, of CibaSpecialty Chemicals Inc.) is charged with the stabilizers listed inTable 20 and is mixed for 2 minutes in a Henschel mixer. This mixture isthen extruded in a twin-screw extruder (type Berstorff) at a maximum of250° C. and is then granulated. In an injection moulding apparatus, thegranulate so obtained is moulded at a maximum of 260° C. to little rods4×6 mm thick and 50 mm long. These little rods are then aged in acirculating air oven at 160° C. After 360 hours the impact strength ofthe rods is measured in KJ/m². The higher the values, the better thestabilization. The results are compiled in Table 20.

TABLE 20 Impact strength in the oven-ageing test at 160° C. Impactstrength in KJ/m² Example Stabilizers after 0 h after 360 h 18a^(i) —130  26 18b^(i) 0.05% Irganox ®245^(o) 132 111 18c^(i) 0.10%Irganox ®245^(o) 135 114 18d^(i) 0.05% Irganox ®245^(o) 134 110 0.05%Irgafos ®168^(a) 18e^(k) 0.05% Irganox ®245^(o) 133 130 0.05%Irgafos ®168^(a) 0.02% compound (109)^(d) For footnotes ^(a), ^(i), ^(k)and ^(o) see the end of Table 25.

EXAMPLE 19 Stabilization of Polycarbonate

1.0 kg of a polycarbonate powder which has been dried for 8 hours at120° C. in a vacuum drying oven (Lexan®145, of General Electric) ischarged with the stabilizers listed in Table 21 and is mixed for 2minutes in a Henschel mixer. This mixture is then extruded in aSchwabenthan extruder at a maximum of 280° C. The polymer string is thengranulated. Using an injection moulding machine, plates having a layerthickness of 2 mm are then moulded from the granulate so obtained at amaximum of 300° C. These plates are then irradiated in a Weather-O-Meter(WOM CI 65) for 2500 hours at a black standard temperature of 63° C., ata dry/wet cycle of 102/18 minutes and at an intensity of 0.35 W/m² at340 nm. The yellowness index (YI) of these plates is then determinedaccording to ASTM D 1925-70. Low YI values denote little discoloration,high YI values high discoloration of the plates. The less discoloration,the more effective the stabilizer or the stabilizer mixture. The resultsare compiled in Table 21.

TABLE 21 Yellowness index after 2500 h Example Stabilizers exposure tolight 19a^(i) — 30.2 19b^(i) 0.30% Tinuvin ®234^(p) 17.8 19c^(i) 0.30%Tinuvin ®360^(q) 16.6 19d^(i) 0.30% Tinuvin ®1577^(r) 11.2 19e^(k) 0.30%Tinuvin ®234^(p) 16.5 0.02% Compound (102) 19f^(k) 0.30%Tinuvin ®360^(q) 15.0 0.02% Compound (102) 19g^(k) 0.30%Tinuvin ®1577^(r)  9.5 0.02% Compound (102) 19h^(k) 0.30%Tinuvin ®234^(p) 13.4 0.05% Irgafos ®168^(a) 0.02% Compound (102)19i^(k) 0.30% Tinuvin ®360^(q) 12.0 0.05% Irgafos ®168^(a) 0.02%Compound (102) 19j^(k) 0.30% Tinuvin ®1577^(r)  9.2 0.05%Irgafos ®168^(a) 0.02% Compound (101) For footnotes ^(a), ^(i), ^(k),^(p), ^(q) and ^(r) see the end of Table 25.

EXAMPLE 20 Stabilization of Polycarbonate

1.0 kg of a polycarbonate powder which has been dried for 8 hours at120° C. in a vacuum drying oven (Lexan®145, of General Electric) ischarged with the stabilizers listed in Table 22 and is then mixed for 2minutes in a Henschel mixer. This mixture is then extruded in aSchwabenthan extruder at a maximum of 280° C. The polymer string is thengranulated. The granulate so obtained is packed into 1 cm thickpolystyrene boxes and the yellowness index (YI) is determined accordingto ASTM D 1925-70. Low YI values denote little discoloration, high YIvalues high discoloration of the samples. The less discoloration, themore effective the stabilizer or the stabilizer mixture. The results arecompiled in Table 22.

TABLE 22 Example Stabilizers Yellowness index 6a^(i) — 10.3 6b^(i) 0.05%GSY ®P101^(s)  5.1 6c^(k) 0.04% GSY ®P101^(s)  1.0 0.02% Compound (104)For footnotes ^(i), k and ^(s) see the end of Table 25.

EXAMPLE 21 Stabilization of Polyesters

2.5 kg of a polyester which has been dried for 12 hours at 120° C. in avacuum drying oven (Polyclear® T86, of Hoechst) is charged with thestabilizers listed in Table 23 and is mixed for 2 hours in a Henschelmixer. This mixture is then extruded in a Schwabenthan extruder at amaximum of 275° C. The polymer string is then granulated. The granulateso obtained is dried for another 12 hours in a vacuum drying oven. In adouble determination, 500 mg of the granulate is heated over 10 minutesto 290° C. and is stored for 1 hour under pure oxygen in a rancimate at290° C. The resulting gaseous separation products are continuously ledinto an aqueous collecting solution and the conductivity (μS) of thissolution is continuously measured. Low conductivity values signify thatfew separation products are formed, high conductivity values signifythat very many separation products are formed. The lower theconductivity values, the more effective the stabilizer. The results arecompiled in Table 23.

TABLE 23 Example Stabilizers Conductivity (μS) 21a^(i) — 47 21b^(k)0.20% Compound (107) 34 For footnotes ^(i) and ^(k) see the end of Table25.

EXAMPLE 22 Stabilization of Light-colored SBR-vulcanisate (OzoneAtmosphere for 48 Hours)

100 parts by weight of Cariflex®S-1502 (styrene/butadiene rubber, Shell)are processed at 60° C., in a mixing mill, with 30.0 parts by weight ofKronos®CL 220 [titanium dioxide (pigment), Kronos Titan GmbH], 30.0parts by weight of Aktisil®MM [kaolin (filler), Hoffmann Mineral,Neuburg/Donau], 5.0 parts by weight of Naftolen®N 401 [plasticizer,Metallgesellschaft], 10.0 parts by weight of zinc oxide [vulcanizationactivator], 2.0 parts by weight of stearic acid [vulcanizationactivator], 2.0 parts by weight of sulfur [vulcanizing agent], 1.0 partby weight of Vulkacit®MOZ [vulcanisation accelerator, Bayer], 0.25 partby weight of Vulkacit®Thiuram [vulcanization accelerator, Bayer] and 1.0part by weight of the stabilizer to be tested according to Table 24, toform a homogeneous mixture, the vulcanization system (sulfur,Vulkacit®MOZ and Vulkacit®Thiuram) not being added until the end of themixing process. The mixture is vulcanized in electrical vulcanizationpresses at 150° C. until T95 is reached in the rheometer curves to formelastomer plates 2 mm thick, 21 cm long and 8.0 cm wide.

Some of the elastomer plates so obtained are tested for the action ofozone according to the ASTM standard D 3395-86 while subject to dynamicelongation. In this test, the plates are first stored for 30 days in astandard atmosphere [23/50 SN-ISO 291]. Test specimens measuring 20 cmby 1 cm are then punched out and exposed to an ozone atmosphere for 48hours (ozone content: 50 pphm; temperature: 40° C.; humidity: 50% rel.;elongation: 0 to 25%; elongation rate: 0.5 Hz; number of load cycles:approximately 173 000). The test plates are then assessed for crackformation according to ASTM D 3395-86. Grade 0 denotes no cracks; grade1 denotes narrow flat cracks; grade 2 denotes moderately broad,moderately deep cracks, clearly visible; grade 3 denotes broad and deepcracks. The lower the grade number, the better the stabilization of theelastomer plates. The results are compiled in Table 24.

The remaining elastomer plates are stored for 3 weeks at roomtemperature in a standard laboratory atmosphere in diffuse daylight. TheΔL-color of those plates is then determined according to DIN 6167, whichcorresponds to a scale of from 0 to 100. No discoloration is indicatedby a value of 100. The results are compiled in Table 24.

TABLE 24 Crack formation ΔL-color according to according to ExamplesStabilizer ASTM D 3395-86 DIN 6167 Example — grade 1-2 94 22a^(i)Example 1.0 phr^(u) Vulkanox ® 4010^(t) grade 0 70 22b^(i) Example 1.0phr^(u) Compound (108) grade 0-1 96 22c^(k) For footnotes ^(i), ^(k),^(t) and ^(u) see the end of Table 25.

EXAMPLE 23 Stabilisation of Light-colored SBR-vulcanisate (OzoneAtmosphere for 96 Hours)

100 parts by weight of Cariflex®S-1502 (styrene/butadiene rubber, Shell)are processed at 60° C., in a mixing mill, with 30.0 parts by weight ofKronos®CL 220 [titanium dioxide (pigment), Kronos Titan GmbH], 30.0parts by weight of Aktisil®MM [kaolin (filler), Hoffmann Mineral,Neuburg/Donau], 5.0 parts by weight of Naftolen®N 401 [plasticiser,Metallgesellschaft], 10.0 parts by weight of zinc oxide [vulcanizationactivator], 2.0 parts by weight of stearic acid [vulcanizationactivator], 2.0 parts by weight of sulfur [vulcanizing agent], 1.0 partby weight of Vulkacit®MOZ [vulcanization accelerator, Bayer], 0.25 partby weight of Vulkacit®Thiuram [vulcanization accelerator, Bayer] and 1.0part by weight of the stabilizer to be tested according to Table 25, toform a homogeneous mixture, the vulcanization system (sulfur,Vulkacit®MOZ and Vulkacit®Thiuram) not being added until the end of themixing process. The mixture is vulcanized in electrical vulcanizationpresses at 150° C. until T95 is reached in the rheometer curves to formelastomer plates 2 mm thick, 21 cm long and 8.0 cm wide.

Some of the elastomer plates so obtained are tested for the action ofozone according to the ASTM standard D 3395-86 while subject to dynamicelongation. In this test the plates are first stored for 30 days in astandard atmosphere [23/50 SN-ISO 291]. Test specimens measuring 20 cmby 1 cm are then punched out and exposed to an ozone atmosphere for 96hours (ozone content: 50 pphm; temperature: 40° C.; humidity: 50% rel.;elongation: 0 to 25%; elongation rate: 0.5 Hz; number of load cycles:approximately 173 000). The test plates are then assessed for crackformation according to ASTM D 3395-86. Grade 0 denotes no cracks; grade1 denotes narrow flat cracks; grade 2 denotes moderately broad,moderately deep cracks, clearly visible; grade 3 denotes broad and deepcracks. The lower the grade number, the better the stabilization of theelastomer plates. The results are compiled in Table 25.

The remaining elastomer plates are stored for 3 weeks at roomtemperature in a standard laboratory atmosphere in diffuse daylight. TheΔL-color of those plates is then determined according to DIN 6167, whichcorresponds to a scale of from 0 to 100. No discoloration is indicatedby a value of 100. The results are compiled in Table 25.

TABLE 25 Crack formation ΔL-color according to according to ExamplesStabilizer ASTM D 3395-86 DIN 6167 Example — grade 2 97 23a^(i) Example2.0 phr^(u) Vulkanox ® 4010^(t) grade 0 56 23b^(i) Example 2.0 phr^(u)compound 101 grade 1 95 23c^(k) Example 2.0 phr^(u) compound 106 grade 195 23d^(k) Example 2.0 phr^(u) compound 108 grade 1 95 23e^(k)^(a)Irgafos ®168 (Ciba Specialty Chemicals Inc.) istris(2,4-di-tert-butylphenyl)phosphite. ^(b)Sandostab ®P-EPQ (Clariant)is tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite.^(c)Irganox ®5057 (Ciba Specialty Chemicals Inc.) is a secondary amineantioxidant and is a technical mixture, obtained by reaction ofdiphenylamine with diisobutylene, comprising ^(a′)3% of diphenylamine;^(b′)14% of 4-tert-butyldiphenylamine; ^(c′)30% of compounds of thegroup ^(i)4-tert-octyldiphenylamine,^(ii)4,4′-di-tert-butyldiphenylamine,^(iii)2,4,4′-tris-tert-butyldiphenylamine; ^(d′)29% of the compounds ofthe group ^(i)4-tert-butyl-4′-tert-octyldiphenylamine, ^(ii)o,o′-, m,m′-or p,p′-di-tert-octyldiphenylamine,^(iii)2,4-di-tert-butyl-4′-tert-octyldiphenylamine; ^(e′)24% of thecompounds of the group ^(i)4,4′-di-tert-octyldiphenylamine and^(ii)2,4-di-tert-octyl-4′-tert-butyldiphenylamine. ^(d)Irganox ®1135(Ciba Specialty Chemicals Inc.) is a phenolic antioxidant of the formulaA-1.

e) Tinuvin®622 (Ciba Specialty Chemicals Inc.) is a compound of theformula H1 in which the average molecular weight is about 3000.

f) Chimassorb®944 (Ciba Specialty Chemicals Inc.) denotes linear orcyclic condensation products prepared fromN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine and is a compound of theformula H2 in which the average molecular weight is about 2500.

g) Chimassorb®119 (Ciba Specialty Chemicals Inc.) denotes condensationproducts prepared from2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane and is a compound of the formulaH3

 in which R′=

h) Irgafos®38 (Ciba Specialty Chemicals Inc.) is a compound of theformula P-1.

i) Comparison Example.

k) Example of this invention.

l) Irganox®1010 (Ciba Specialty Chemicals Inc.) denotes thepentaerythritol ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid.

m) HALS mixture is a 1:1 mixture of Tinuvin®622 [Ciba SpecialtyChemicals Inc.; see footnote e)] and Chimassorb®119 (Ciba SpecialtyChemicals Inc.; see footnote g)].

n) Irganox®1076 (Ciba Specialty Chemicals Inc.) denotes a compound offormula A-2.

o) Irganox®245 (Ciba Specialty Chemicals Inc.) denotes a compound offormula A-3.

p) Tinuvin®234 (Ciba Specialty Chemicals Inc.) denotes a compound offormula UV-1.

q) Tinuvin®360 (Ciba Specialty Chemicals Inc.) denotes a compound offormula UV-2.

r) Tinuvin®1577 (Ciba Specialty Chemicals Inc.) denotes a compound offormula UV-3.

s) GSY® P101 (Yoshitomi) denotes a compound of formula P-2.

t) Vulkanox®4010 (Bayer) denotes 4-isopropylamino-diphenylamine offormula A.

u) phr denotes “parts per hundred of rubber”.

What is claimed is:
 1. A compound of the formula I

wherein, when n is 1, R₁ is a radical of the formula II, III or IV

 and when n is 2, R₁ is

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,chloro, hydroxyl, C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₄alkylamino,di-(C₁-C₄alkyl)amino, C₁-C₂₅alkanoyloxy, C₁-C₂₅alkanoylamino,C₃-C₂₅alkenoyloxy, C₃-C₂₅alkanoyloxy which is interrupted by oxygen,sulfur or

C₆-C₉cycloalkylcarbonyloxy, benzoyloxy or C₁-C₁₂alkyl-substitutedbenzoyloxy; or each pair of substituents R₂ and R₃ or R₃ and R₄ or R₄and R₅ together with the linking carbon atoms, forms a benzene ring; orR₄ is additionally —(CH₂)_(p)—COR₁₉ or —(CH₂)_(q)OH, or when R₃, R₅ andR₆ are hydrogen, R₄ is additionally a radical of the formula V

wherein R₁ is as defined above for n=1, R₆ is hydrogen or a radical ofthe formula VI

in which R₄ is not a radical of the formula V and R₁ is as defined abovefor n=1, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are eachindependently of one another hydrogen, fluoro, fluoro-substitutedC₁-C₁₂alkyl; —CN,

—SOR₂₆, —SO₂R₂₆ or SO₃R₂₆; with the proviso that at least one of R₇, R₈,R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ or R₁₅ is not hydrogen, R₁₆ and R₁₇ are eachindependently of one another phenylene or naphthylene which aresubstituted by fluoro, fluoro-substituted C₁-C₁₂alkyl, —CN,

—SOR₂₆, —SO₂R₂₆ or SO₃R₂₆, R₁₈ is hydrogen or C₁-C₈alkyl, R₁₉ ishydroxyl,

C₁-C₁₈alkoxy or

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃,C₁-C₁₂alkyl or phenyl, or R₂₀ and R₂₁ together with the linking carbonatom, form a C₅-C₈cycloalkylidene ring which is unsubstituted orsubstituted by 1 to 3 C₁-C₄alkyl groups; R₂₂ is hydrogen, hydroxyl,

C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted or C₁-C₄alkyl-substitutedphenyl; unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl; orC₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

R₂₃ is C₁-C₂₅alkyl, C₇-C₉phenylalkyl, unsubstituted orC₁-C₄alkyl-substituted phenyl; unsubstituted or C₁-C₄alkyl-substitutedC₅-C₈cycloalkyl; or C₃-C₂₅alkyl which is interrupted by oxygen, sulfuror

R₂₄ and R₂₅ are each independently of one another hydrogen, C₁-C₂₅alkyl,hydroxyl-substituted C₂-C₂₄alkyl; C₃-C₂₅alkyl which is interrupted byoxygen, sulfur or

phenylalkyl which is unsubstituted or is substituted on the phenyl ringby C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₂₄ and R₂₅, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring which is unsubstituted or is substituted by C₁-C₄alkylor is interrupted by oxygen, sulfur or

R₂₆ is hydrogen or C₁-C₂₅alkyl, R₂₇ and R₂₈ are each independently ofone another hydrogen, C₁-C₂₅alkyl, hydroxyl-substituted C₂-C₂₄alkyl;C₃-C₂₅alkyl which is interrupted by oxygen, sulfur or

phenylalkyl which is unsubstituted or is substituted on the phenyl ringby C₁-C₄alkyl; or C₃-C₂₄alkenyl; or R₂₇ and R₂₈, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring which is unsubstituted or is substituted by C₁-C₄alkylor is interrupted by oxygen, sulfur or

R₂₉ and R₃₀ are each independently of one another hydrogen, C₁-C₁₈alkylor C₇-C₉phenylalkyl, or R₂₉ and R₃₀ together with the nitrogen atom towhich they are attached form a 5-, 6- or 7-membered heterocyclic ringwhich is unsubstituted or is substituted by C₁-C₄alkyl or is interruptedby oxygen, sulfur or

X₁ is a direct bond, C₁-C₁₈alkylene, C₂-C₁₈alkylene which is interruptedby oxygen, sulfur or

C₂-C₁₈alkenylene, C₂-C₂₀alkylidene, C₇-C₂₀phenylalkylidene,C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene, unsubstituted orC₁-C₄alkyl-substituted phenylene,

or —O—X₃—O—, X₂ is C₂-C₁₈alkylene, C₄-C₁₈alkylene which is interruptedby oxygen, sulfur or

C₂-C₁₈alkenylene, C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene,unsubstituted or C₁-C₄alkyl-substituted phenylene,

X₃ is C₂-C₁₈alkylene, C₄-C₁₈alkylene which is interrupted by oxygen,sulfur or

C₂-C₁₈alkenylene, C₅-C₈cycloalkylene, C₇-C₈bicycloalkylene,unsubstituted or C₁-C₄alkyl-substituted phenylene,

M is a metal cation of valency r, n is 1 or 2, p is 0, 1 or 2, q is 1,2, 3, 4, 5 or 6, and r is 1, 2 or
 3. 2. A compound according to claim 1,wherein, when n is 1, R₁ is a radical of the formula II, III or IV

and when n is 2, R₁ is

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,chloro, hydroxyl, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl,C₅-C₈cycloalkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkylthio, C₁-C₁₈alkanoyloxy,C₁-C₁₈alkanoylamino, C₃-C₁₈alkenoyloxy, C₃-C₁₈alkanoyloxy which isinterrupted by oxygen or sulfur; C₆-C₉cycloalkylcarbonyloxy, benzoyloxyor C₁-C₄alkyl-substituted benzoyloxy; or each pair of substituents R₂and R₃ or R₃ and R₄ or R₄ and R₅ together with the linking carbon atoms,forms a benzene ring; or R₄ is additionally —(CH₂)_(p)—COR₁₉ or—(CH₂)_(q)OH, or when R₃, R₅ and R₆ are hydrogen, R₄ is additionally aradical of the formula V

wherein R₁ is as defined above for n=1, R₆ is hydrogen or a radical ofthe formula VI

in which R₄ is not a radical of the formula V and R₁ is as defined abovefor n=1, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are eachindependently of one another hydrogen, fluoro, fluoro-substitutedC₁₋C₈alkyl; —CN,

—SOR₂₆, —SO₂R₂₆ or SO₃R₂₆; with the proviso that at least one of R₇, R₈,R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ or R₁₅ is not hydrogen, R₁₆ and R₁₇ are eachindependently of one another phenylene or naphthylene which aresubstituted by fluoro, trifluoromethyl, —CN,

—SOR₂₆, —SO₂R₂₆ or SO₃R₂₆, R₁₈ is hydrogen or C₁-C₄alkyl, R₁₉ ishydroxyl,

C₁-C₁₈alkoxy or

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃,C₁-C₈alkyl or phenyl, or R₂₀ and R₂₁ together with the linking carbonatom, form a C₅-C₈cycloalkylidene ring; R₂₂ is hydrogen, hydroxyl,

C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, C₅-C₈cycloalkyl; or C₃-C₂₅alkylwhich is interrupted by oxygen or sulfur, R₂₃ is C₁-C₂₂alkyl,C₇-C₉phenylalkyl, phenyl, C₅-C₈cycloalkyl or C₃-C₂₅alkyl which isinterrupted by oxygen or sulfur, R₂₄ and R₂₅ are each independently ofone another hydrogen, C₁-C₁₈alkyl, hydroxyl-substituted C₂-C₁₈alkyl;C₃-C₁₈alkyl which is interrupted by oxygen, sulfur or

phenylalkyl, or C₃-C₁₈alkenyl; or R₂₄ and R₂₅, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring, R₂₆ is hydrogen or C₁-C₁₈alkyl, R₂₇ and R₂₈ are eachindependently of one another hydrogen, C₁-C₁₈alkyl, hydroxyl-substitutedC₂-C₁₈alkyl; C₃-C₁₈alkyl which is interrupted by oxygen, sulfur or

phenylalkyl, or C₃-C₁₈alkenyl; or R₂₇ and R₂₈, together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic ring, R₂₉ and R₃₀ are each independently of one anotherhydrogen, C₁-C₁₈alkyl or C₇-C₉phenylalkyl, or R₂₉ and R₃₀ together withthe nitrogen atom to which they are attached form a 5-, 6- or 7-memberedheterocyclic ring, X₁ is a direct bond, C₁-C₁₂alkylene, C₂-C₁₈alkylenewhich is interrupted by oxygen or sulfur; C₂-C₁₂alkenylene,C₂-C₁₂alkylidene, C₇-C₁₂phenylalkylidene, C₅-C₈cycloalkylene, phenylene,

or —O—X₃—O—, X₂ is C₂-C₁₂alkylene, C₄-C₁₂alkylene which is interruptedby oxygen, sulfur or

C₂-C₁₂alkenylene, C₅-C₈cycloalkylene, phenylene,

X₃ is C₂-C₁₈alkylene, C₄-C₁₂alkylene which is interrupted by oxygen,sulfur or

C₂-C₁₂alkenylene, C₅-C₈cycloalkylene, phenylene,

M is a metal cation of valency r, n is 1 or 2, p is 0, 1 or 2, q is 1,2, 3, 4, 5 or 6, and r is 1, 2 or
 3. 3. A compound according to claim 1,wherein, when n is 1, R₁ is a radical of the formula II, III or IV, andwhen n is 2, R₁ is

R₂, R₃, R₄ and R₅ are each independently of one another hydrogen,C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl, C₁-C₁₂alkoxy,C₁-C₁₂alkylthio, C₁-C₁₂alkanoyloxy, C₃-C₁₂alkenoyloxy, C₃-C₁₂akanoyloxywhich is interrupted by oxygen; cyclohexylcarbonyloxy, benzoyloxy oreach pair of substituents R₂ and R₃ or R₃ and R₄ or R₄ and R₅ togetherwith the linking carbon atoms, forms a benzene ring; or R₄ isadditionally —(CH₂)_(p)—COR₁₉ or —(CH₂)_(q)OH, or when R₃, R₅ and R₆ arehydrogen, R₄ is additionally a radical of the formula V, wherein R₁ isas defined above for n=1, R₆ is hydrogen or a radical of the formula VIin which R₄ is not a radical of the formula V and R₁ is as defined abovefor n=1, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are eachindependently of one another hydrogen, fluoro, fluoro-substitutedC₁-C₄alkyl; —CN,

—SOR₂₆, —SO₂R₂₆ or SO₃R₂₆; with the proviso that at least one of R₇, R₈,R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ or R₁₅ is not hydrogen, R₁₆ and R₁₇ are eachindependently of one another phenylene or naphthylene, R₁₉ is hydroxyl,C₁-C₁₈alkoxy or

R₂₀ and R₂₁ are each independently of one another hydrogen, CF₃ orC₁-C₄alkyl, or R₂₀ and R₂₁ together with the linking carbon atom, form acyclohexylidene ring; R₂₂ is hydroxyl, C₁-C₁₂alkyl, phenyl, cyclohexylor C₃-C₁₂alkyl which is interrupted by oxygen, R₂₃ is C₁-C₂₂alkyl,benzyl, phenyl, cyclohexyl or C₃-C₁₂alkyl which is interrupted byoxygen, R₂₄ and R₂₅ are each independently of one another hydrogen,C₁-C₁₂alkyl, hydroxyl-substituted C₂-C₁₂alkyl; C₃-C₁₂alkyl which isinterrupted by oxygen; benzyl or C₃-C₁₂alkenyl; or R₂₄ and R₂₅, togetherwith the nitrogen atom to which they are attached, form 6-memberedheterocyclic ring, R₂₆ is C₁-C₁₂alkyl, R₂₇ and R₂₈ are eachindependently of one another hydrogen, C₁-C₁₂alkyl, hydroxyl-substitutedC₂-C₁₂alkyl; C₃-C₁₈alkyl which is interrupted by oxygen; benzyl orC₃-C₁₂alkenyl; or R₂₇ and R₂₈, together with the nitrogen atom to whichthey are attached, form 6-membered heterocyclic ring, R₂₉ and R₃₀ areeach independently of one another hydrogen, C₁-C₁₂alkyl or benzyl, orR₂₉ and R₃₀ together with the nitrogen atom to which they are attachedform a 6-membered heterocyclic ring, X₁ is a direct bond, C₁-C₈alkylene,C₂-C₁₈alkylene which is interrupted by oxygen; phenylene,

or —O—X₃—O—, X₂ is C₂-C₈alkylene, C₄-C₁₂alkylene which is interrupted byoxygen; cyclohexylene, phenylene,

X₃ is C₂-C₁₈alkylene, C₄-C₁₂alkylene which is interrupted by oxygen;C₂-C₁₂alkenylene, cyclohexylene, phenylene,

n is 1 or 2, p is 1 or 2, and q is 2 or
 3. 4. A compound according toclaim 1, wherein, when n is 1, R₁ is a radical of the formula II, andwhen n is 2, R₁ is

R₂ is hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl,C₁-C₈alkanoyloxy or benzoyloxy, R₃ is hydrogen or C₁-C₄alkyl, R₄ ishydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl, cyclohexyl,C₁-C₈alkanoyloxy, —(CH₂)_(p)—COR₁₉ or —(CH₂)_(q)OH, or when R₃, R₅ andR₆ are hydrogen, R₄ is additionally a radical of the formula V, whereinR₁ is as defined above for n=1, R₅ is hydrogen or C₁-C₄alkyl, R₆ ishydrogen or a radical of the formula VI in which R₄ is not a radical ofthe formula V and R₁ is as defined above for n=1, R₇, R₈, R₉, R₁₀ andR₁₁ are each independently of one another hydrogen, fluoro,fluoro-substituted C₁-C₄alkyl; —CN,

—SOR₂₆, or —SO₂R₂₆; with the proviso that at least one of R₇, R₈, R₉,R₁₀ or R₁₁ is not hydrogen, R₁₆ and R₁₇ are each independently of oneanother phenylene or naphthylene, R₁₉ is C₁-C₈alkoxy, R₂₀ and R₂₁ areeach independently of one another hydrogen, CF₃ or C₁-C₄alkyl, or R₂₀and R₂₁ together with the linking carbon atom, form a cyclohexylidenering; R₂₃ is C₁-C₂₂alkyl, benzyl, phenyl, cyclohexyl or C₃-C₁₂alkylwhich is interrupted by oxygen, R₂₄ and R₂₅ are each independently ofone another hydrogen, C₁-C₄alkyl, hydroxyl-substituted C₂-C₄alkyl;C₃-C₁₂alkyl which is interrupted by oxygen; benzyl or C₃-C₁₂alkenyl, R₂₆is C₁-C₈alkyl, R₂₉ and R₃₀ are each independently of one anotherhydrogen, C₁-C₈alkyl or benzyl, X₁ is a direct bond, C₁-C₈alkylene,

or —O—X₃—O—, X₂ is C₂-C₈alkylene or C₄-C₁₂alkylene which is interruptedby oxygen, X₃ is C₂-C₁₈alkylene or C₄-C₁₂alkylene which is interruptedby oxygen, n is 1 or 2, p is 1 or 2, and q is 2 or
 3. 5. A compoundaccording to claim 1, wherein, when n is 1, R₁ is a radical of theformula II, and when n is 2, R₁ is

R₂ is C₁-C₁₈alkyl, C₇-C₉phenylalkyl, phenyl or cyclohexyl, R₃ ishydrogen or methyl, R₄ is hydrogen, C₁-C₁₈alkyl, C₇-C₉phenylalkyl,phenyl, cyclohexyl or a radical of the formula V, wherein R₁ is asdefined above for n=1, R₅ is hydrogen or methyl, R₆ is hydrogen or aradical of the formula VI in which R₄ is not a radical of the formula Vand R₁ is as defined above for n=1, R₇, R₈, R₉, R₁₀ and R₁₁ are eachindependently of one another hydrogen, fluoro, fluoro-substitutedC₁-C₄alkyl; —CN,

—SOR₂₆, or —SO₂R₂₆; with the proviso that at least one of R₇, R₈, R₉,R₁₀ or R₁₁ is not hydrogen, R₁₆ and R₁₇ are each independently of oneanother phenylene or naphthylene, R₂₀ and R₂₁ are each independently ofone another hydrogen or C₁-C₄alkyl, or R₂₀ and R₂₁ together with thelinking carbon atom, form a cyclohexylidene ring; R₂₃ is C₁-C₂₂alkyl,benzyl, phenyl, cyclohexyl or C₃-C₁₂alkyl which is interrupted byoxygen, R₂₆ is C₁-C₈alkyl, X₁ is a direct bond, C₁-C₈alkylene or—O—X₃—O—, X₃ is C₂-C₁₈alkylene or C₄-C₁₂alkylene which is interrupted byoxygen, and n is 1 or
 2. 6. A compound according to claim 1, wherein,when n is 1, R₁ is a radical of the formula II, and when n is 2, R₁ is

R₂ is C₁-C₈alkyl or cyclohexyl, R₃ is hydrogen, R₄ is hydrogen,C₁-C₈alkyl, cyclohexyl or a radical of the formula V, wherein R₁ is asdefined above for n=1, R₅ is hydrogen, R₆ is hydrogen or a radical ofthe formula VI in which R₄ is not a radical of the formula V and R₁ isas defined above for n=1, R₇, R₈, R₉, R₁₀ and R₁₁ are each independentlyof one another hydrogen, fluoro, trifluoromethyl; —CN or

with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ is nothydrogen, R₁₆ and R₁₇ are each independently of one another phenylene ornaphthylene, R₂₀ and R₂₁ are each independently of one another hydrogenor C₁-C₄alkyl, or R₂₀ and R₂₁ together with the linking carbon atom,form a cyclohexylidene ring; R₂₃ is C₁-C₂₂alkyl, benzyl or cyclohexyl,X₁ is C₁-C₈alkylene or —O—X₃—O—, X₃ is C₂-C₁₄alkylene, and n is 1 or 2.7. A compound according to claim 1, wherein when n is 1, R₁ is a radicalof the formula II, and when n is 2, R₁ is

R₂ is C₁-C₄alkyl, R₃ is hydrogen, R₄ is C₁-C₄alkyl, R₅ is hydrogen, R₆is hydrogen or a radical of the formula VI wherein R₁ is as definedabove for n=1, R₇ is hydrogen or trifluoromethyl, R₈ is hydrogen,trifluoromethyl or —CN, R₉ is hydrogen or trifluoromethyl, R₁₀ ishydrogen, trifluoromethyl or —CN, R₁₁ is hydrogen, fluoro,trifluoromethyl, —CN or

with the proviso that at least one of R₇, R₈, R₉, R₁₀ or R₁₁ is nothydrogen, R₁₆ and R₁₇ are phenylene or naphthylene, R₂₃ is C₁-C₂₂alkyl,X₁ is —O—X₃—O—, X₃ is C₄-C₁₂alkylene, and n is 1 or
 2. 8. A compositioncomprising a) an organic material which is susceptible to oxidative,thermal or light-induced degradation, and b) at least one compound ofthe formula I according to claim
 1. 9. A composition according to claim8, wherein component (a) is selected from the group consisting of alubricant, a fuel, a hydraulic fluid, a metal-working fluid and anatural, semi-synthetic or synthetic polymer.
 10. A compositionaccording to claim 8, comprising as component (a) an engine oil, aturbine oil, a gear oil, a diesel fuel or a lubricating grease.
 11. Acomposition according to claim 8, comprising as component (a) asynthetic polymer.
 12. A composition according to claim 8, whereincomponent (b) is present in an amount of from 0.0005 to 10%, based onthe weight of component (a).
 13. A composition according to claim 8,comprising in addition, besides components (a) and (b), furtheradditives.
 14. A composition according to claim 13, comprising asfurther additives phenolic antioxidants, light-stabilizers and/orprocessing stabilizers.
 15. A process for stabilizing an organicmaterial against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein or applying thereto at least onecompound of the formula I according to claim
 1. 16. A color photographicmaterial comprising a compound of formula I according to claim
 1. 17. Acolor photographic material according to claim 16, comprising thecompound of the formula I in a non-photosensitive interlayer.
 18. Acolor photographic material according to claim 16, comprising thecompound of the formula I in an amount from 10 to 1000 mg/m².
 19. Aprocess for preventing migration of the oxidized developer in a colorphotographic material from one color sensitive layer to another byincorporating a compound of the formula I according to claim 1 into saidmaterial.